CN1590302A - Coprecipitation method for preparing ultra fine zinc oxide powder possessing high electric conductivity - Google Patents
Coprecipitation method for preparing ultra fine zinc oxide powder possessing high electric conductivity Download PDFInfo
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- CN1590302A CN1590302A CN 200310121344 CN200310121344A CN1590302A CN 1590302 A CN1590302 A CN 1590302A CN 200310121344 CN200310121344 CN 200310121344 CN 200310121344 A CN200310121344 A CN 200310121344A CN 1590302 A CN1590302 A CN 1590302A
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- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000000975 co-precipitation Methods 0.000 title claims abstract description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims description 61
- 239000000843 powder Substances 0.000 claims abstract description 35
- 238000002360 preparation method Methods 0.000 claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012266 salt solution Substances 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 11
- 239000011701 zinc Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 229910052786 argon Inorganic materials 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 4
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052738 indium Inorganic materials 0.000 claims abstract description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 239000010703 silicon Substances 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 239000001099 ammonium carbonate Substances 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 239000011787 zinc oxide Substances 0.000 description 19
- 229960001296 zinc oxide Drugs 0.000 description 19
- 238000005259 measurement Methods 0.000 description 12
- 238000005245 sintering Methods 0.000 description 11
- 239000012808 vapor phase Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- -1 nitrate Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Abstract
The invention relates to a preparation method for preparing nano-scale oxidized zinc powder with high conductivity. The method simultaneously drip mixed salt solution of zincic soluble salt and doping elements such as aluminum, gallium, indium, Yt, scandium, tin, germanium, silicon, as well as precipitating agent into water, to generate coprecipitation to generate doped zinc bloom precursor basic zinc carbonate in condition of controlling temperature and PH value of entire reaction system, and at last, calcining the product in mixed gas atmospheres of hydrogen gas and argon gas, doped superfine zinc bloom conductive powder material can be obtained. The powder material prepared by the invention has small particle-size, uniform grain fineness distribution, and which mean particle diameter is about 10 to 80 nanometer. The electric volume resistivity of the powder can reach 2.5*10^-3 omega.cm, thus its electro conductivity is better than the sample prepared by plasma method and gas-phase method in current market. The preparation method further enhances whiteness degree and conductivity of the oxidized zinc powder, and further reduces the cost.
Description
Technical field
The present invention relates to a kind of preparation method of Zinc oxide powder, relate in particular to the method that a kind of preparation has the nano grade inorganic oxide powder of high conductivity.
Background technology
Along with the raising with people's living standard of developing rapidly of electronic industry, the electroconductibility powder is as a kind of functional filler in the preparation process such as plastics, coating, fiber, has performances such as antistatic, electromagnetic shielding, begun to cause people's extensive concern.At present the electroconductibility powder mainly contains: metal-powder is as silver, nickel etc., non-metallic powder such as graphite, carbon black etc., and metal oxide such as zinc oxide, weisspiessglanz etc. also have compound powder and iodide such as SnO in addition
2-In
2O
3Coat mica or inorganic mineral powder, cupric iodide etc.The conductivity excellence of metal and carbon black material, but have color because of itself or proportion is bigger, be difficult for disperseing; The chemical stability of polymkeric substance of cupric iodide of having mixed is very poor; The stannic oxide of mixing antimony has good electroconductibility, but the antimony doping makes polymkeric substance have black-and-blue accent, is exactly antimony doping toxigenicity in addition.Because of above-mentioned reason, the application of these materials has been subjected to very big restriction, makes people's sight turn on gradually on the research direction of good dispersion property, nontoxic, whiteness is higher, physical and chemical stability is better and production cost is lower doping zinc-oxide powder.
Traditional method for preparing conductive zinc oxide is that specific metallic compound is added in the Zinc oxide powder such as aluminum oxide or aluminium salt, then mixture is carried out sintering under certain condition and make (Howard M.Cyr, et al.US Patent:3089856,1963; Makoto Muramoto, et al.US Patent:4282117,1981.).The Zinc oxide powder volume specific resistance that this method is prepared is very high, under the best situation also greater than 1.0 * 10
1Ω cm, conductivity is relatively poor, and be that zinc oxide obtains to mix as original material sintering under greater than 750 ℃ high temperature in the reducing atmosphere that hydrogen exists, zinc oxide is because the calcining under reducing atmosphere can have grey and can not show enough whiteness as a result, and the calcining under the high temperature can make Zinc oxide particles grow up to cause the formation of some big particles.The technology of this complexity makes the production cost of its cost much larger than carbon black.Afterwards the co-precipitation preparation method of Chu Xianing also obtained a large amount of research (
Djega-Mariadasson, et al.US Patent:4894185,1990; Takao Hayashi, et al.US Patent:5312614,1994.), generally be tentatively to control under the situation of experiment condition mixing salt solution with zinc directly to be added drop-wise to co-precipitation takes place in the precipitation agent, the effect though ratio solid phase mixing sintering method in the past can obtain to mix relatively preferably, but still cause when precipitation dopant ion and zine ion can not be simultaneously precipitation fully uniformly, doped element can not be doped in the lattice of zinc oxide fully equably, though the method before the particle that obtains mixes is more even, the performance of powder also is greatly improved than the performance of the powder that solid phase mixing sintering method before makes, but the conductivity of the powder that finally obtains is still poor (under the optimal situation, when adopting the optimum doping content of non-ferrous metal Sn and rare earth element Ga, during pH=9.0 the synthetic powder under hydrogen atmosphere in 400 ℃ of sintering 1 hour, can access the conductive zinc oxide powder that volume specific resistance is 7.4 * 10-1 Ω cm), particle size is bigger, and has more serious agglomeration.Vapor phase process (the Yoshimaru of bibliographical information several years ago, et al.US Patent:5560871,1996) and plasma method (Yuan Fangli etc., chemical industry metallurgical, 1998,19 (3): 212-216) performance of the conductive zinc oxide powder of Sheng Chaning (performance perameter of powder sees Table 1) is than very big improvement had been arranged in the past, but equally also exist problems such as whiteness, specific conductivity is on the low side: it is lower that vapor phase process prepares the conductive zinc oxide powder cost, but particle size is in micron order basically, and its particle size is too big for the application in nano-functional material field; And the conductive zinc oxide powder particle size of plasma method preparation is proper, dispersiveness is also fine, but the cost of its preparation is very high again.The problem of these existence all makes being applied in to a great extent of present conductive zinc oxide powder be restricted.
Summary of the invention
The objective of the invention is to overcome above-mentioned existing preparation method's shortcoming, further improve the whiteness and the specific conductivity of Zinc oxide powder, and further reduced cost, thereby a kind of presoma zinc subcarbonate powder that adopts the synthetic doped with metal elements of improved liquid-phase coprecipitation is provided, presoma low-temperature bake under the mixing reducing atmosphere of hydrogen and argon gas is prepared the method for nano-scale oxidized zinc powder with excellent conductive capability.
The object of the present invention is achieved like this:
The invention provides the method that preparation has the nano-scale oxidized zinc powder of excellent conductive capability, comprising:
(1) at first synthetic zinc subcarbonate presoma: soluble salt such as nitrate, muriate or the vitriol of zinc and doped element (comprising aluminium, gallium, indium, yttrium, scandium, tin, germanium, silicon) are mixed with mixing solutions, concentration is 0.5mol/L-5.0mol/L, and the interpolation molar weight of doped element is the 0.1-10.0mol% of zinc and doped element integral molar quantity;
(2) mixing salt solution and the precipitation agent with preparation in the step (1) is added drop-wise in the water together, and to keep the temperature of reaction system in the dropping process be that 40 ℃-75 ℃, pH value are controlled in the 7.0-7.5 scope, applies violent stirring simultaneously; Promptly obtaining even adulterated white zinc subcarbonate precipitation generates; In order to keep the pH value in the entire reaction course constant, drip ammonia soln or the sodium hydroxide solution that the back restock drips 0.5-4.0mol/L in precipitant solution, the mixing salt solution of preparation is added dropwise to complete in step (1); Ageing 0-4 hour, till the pH of whole system value no longer changes;
(3) precipitation that above-mentioned reaction is made oven dry after the routine washing separates, the powder of gained is calcined under the mixed atmosphere of hydrogen and argon gas, and calcining temperature is 400 ℃-700 ℃, and constant temperature time is 0-4 hour, can obtain final conductive zinc oxide powder after the calcining.
The soluble salt of described zinc comprises: zinc nitrate, zinc chloride or zinc sulfate, the purity of salt is at least technical grade.
The soluble salt of described doped element aluminium, gallium, indium, yttrium, scandium, tin, germanium, silicon: nitrate, muriate or vitriol, the purity of salt is at least technical grade.
Described precipitation agent comprises: yellow soda ash, sodium bicarbonate or bicarbonate of ammonia, concentration are 0.5mol/L-4.0mol/L
The volume ratio of hydrogen is the 0.5-100% of total gas volume in the described mixed gas.
The method that preparation provided by the invention has the nano-scale oxidized zinc powder of excellent conductive capability has the following advantages:
Method of the present invention is under the control synthesis condition, adopts the presoma zinc subcarbonate powder of the synthetic doped with metal elements of liquid-phase coprecipitation, and presoma low-temperature bake under the mixing reducing atmosphere of hydrogen and argon gas is made final conductive zinc oxide powder.Mixing salt solution and the precipitation agent common mode that drips under the situation of control synthesis condition produces co-precipitation in the employing liquid phase coprecipitation process, the doping composition can distribute in the presoma precipitation fully equably, this is to prepared a main improvement of conductive zinc oxide method in the past, this makes that also the volume specific resistance of the powder prepare is very low and very stable, minimumly can reach 2.5 * 10
-3Ω cm, conductivity are better than the conductive zinc oxide powder material of vapor phase process and plasma method preparation in the market.Because adopt control synthesis condition and lower maturing temperature, no thick particle generation in the product, particle size is less and be evenly distributed, and the minimum average particle diameters scope can reach 10-30nm.It makes final conductive zinc oxide powder performance reference table 1.Entire reaction course is the synthetic preparation process of general coprecipitation method, and the cost of preparation powder is lower, especially requires can also to adopt lower-cost element such as aluminium to mix when not being very harsh in specific conductivity, and this can further reduce cost again.So Zhi Bei conductive zinc oxide powder in this way, conductivity is good, and granularity is very little can to reach nano level and particle size distribution is even fully, and powder has very high whiteness, do not have toxicity, and preparation cost is also lower.
Embodiment
Embodiment 1
11.044kg Zn (NO
3)
26H
2O, 0.141kg Al (NO
3)
39H
2O (adding proportion of Al is the 1.0mol% of integral molar quantity) is dissolved in and is mixed with mixing salt solution A, 1.987kgNa in 50 premium on currency
2CO
3Be dissolved in 50 premium on currency and be mixed with solution B, A and B are slowly added in 30 premium on currency simultaneously, and the temperature of the whole reaction system of violent stirring, and maintenance simultaneously is 40 ℃ and pH=7.0, the pH value in later stage adds back ageing 4 hours fully with the NaOH preparing solution of 2.0mol/L, A.The throw out of reaction gained after washing, alcohol are washed repeatedly, was dried 48 hours at 75 ℃ after filtration.Throw out after the oven dry the mixed atmosphere (volume ratio of hydrogen is 5.0%) of 600 ℃, hydrogen and argon gas down calcining make final electric conductive oxidation zinc powder after 1.0 hours.
Volume specific resistance is measured
Get the final conductive zinc oxide pressed powder moulding of 5g, pressure is 200MPa/cm
2The compressing tablet diameter is that 30.0mm, thickness are about 3.6mm, measures its resistance behind the aluminium-plated electrode in surface, and final the conversion becomes the volume specific resistance of powder.The final volume specific resistance of measuring powder is 4.5 * 10
-1Ω cm.Consider the influence of different measuring methods simultaneously, measured the volume specific resistance that vapor phase process and plasma method prepare sample simultaneously and be respectively 1.8 * 10 final measurement result
-1Ω cm and 8.0 * 10
-1The measurement result that Ω cm, vapor phase process prepare sample is consistent with the measurement result of document (EP 059,828,4A1 1993), and the volume specific resistance that powder is measured in this explanation in this way still is believable.
Particle size
The particles of powder size is measured by the transmission electron microscope photo, finally estimates the particulate mean sizes by the peak width at half height of the scale associating XRD diffraction curve of photo and is about 80nm-150nm.
Whiteness
The whiteness value of conductive zinc oxide is measured with Elrepho450 type beam split blancometer, and final measurement result is 88.The performance of the conductive zinc oxide of present embodiment preparation is as shown in table 1.
Embodiment 2
10.567kg ZnSO
47H
2O, 0.250kg Al
2(SO
4)
318H
2O, (adding proportion of Al is the 2.0mol% of integral molar quantity) is dissolved in and is mixed with mixing salt solution A, 6.226kg NH in 25 premium on currency
4HCO
3Be dissolved in 50 premium on currency and be mixed with solution B, experimental technique is with embodiment 1, and the NaOH solution of just wherein allocating the pH value changes the NH of 2.0mol/L into
3H
2O solution, pH=7.5, the volume ratio of hydrogen is 100% in the mixed atmosphere when sintering.
The final measurement result of powder is: volume specific resistance is 2.5 * 10
-2Ω cm, whiteness value is 81, particle mean size is about 15nm-40nm.The performance of the conductive zinc oxide of present embodiment preparation is as shown in table 1.
Embodiment 3
Experiment reagent and method are with embodiment 2, and the temperature when just synthetic is 40 ℃, and temperature is 400 ℃ during sintering, and the volume ratio of hydrogen is 10.0% in the mixed atmosphere, and calcination time is 30 minutes.
The final measurement result of powder is: volume specific resistance is 5.5 * 10
-2Ω cm, whiteness value is 85, particle mean size is about 10nm-30nm.The performance of the conductive zinc oxide of present embodiment preparation is as shown in table 1.
Embodiment 4
9.705kg ZnSO
47H
2O, 1.249kg Al
2(SO
4)
318H
2O, (adding proportion of Al is the 10.0mol% of integral molar quantity) is dissolved in and is mixed with mixing salt solution A in 10 premium on currency, additive method is with embodiment 2, temperature when just synthetic is 75 ℃, temperature is 700 ℃ during sintering, during sintering in the mixed atmosphere volume ratio of hydrogen be 10.0%, calcination time is 3 hours.
The final measurement result of powder is: volume specific resistance is 5.4 * 10
1Ω cm, whiteness value is 86, particle mean size is about 60nm-100nm.The performance of the conductive zinc oxide of present embodiment preparation is as shown in table 1.
Embodiment 5
10.567 ZnSO
47H
2O, 0.132kg GaCl
3, (adding proportion of Ga is the 2.0mol% of integral molar quantity) is dissolved in and is mixed with mixing salt solution A, 6.615kg NaHCO in 100 premium on currency
3Be dissolved in 100 premium on currency and be mixed with solution B, the temperature when just synthetic is 40 ℃ to additive method with embodiment 2, and temperature is 450 ℃ during sintering, during sintering in the mixed atmosphere volume ratio of hydrogen be 5.0%, calcination time is 0.5 hour.
The final measurement result of powder is: volume specific resistance is 5.0 * 10
-3Ω .cm, whiteness value is 70, particle mean size is about 15nm-40nm.The performance of the conductive zinc oxide of present embodiment preparation is as shown in table 1.
Embodiment 6
10.729kg ZnSO
47H
2O and 0.049kg ScCl
36H
2O (adding proportion of Sc is the 0.5mol% of integral molar quantity) is dissolved in and is mixed with mixing salt solution A in 25 premium on currency, and additive method is with embodiment 5.
The final measurement result of powder is: volume specific resistance is 5.0 * 10
-1Ω cm, whiteness value is 80, particle mean size is about 15nm-40nm.The performance of the conductive zinc oxide of present embodiment preparation is as shown in table 1.
Embodiment 7
10.567kg ZnSO
47H
2O and 0.287kg Y (NO
3)
36H
2O (adding proportion of Y is the 2.0mol% of integral molar quantity) is dissolved in and is mixed with mixing salt solution A in 25 premium on currency, and additive method is with embodiment 5.
The final measurement result of powder is: volume specific resistance is 3.2 * 10
-1Ω cm, whiteness value is 82, particle mean size is about 10nm-35nm.The performance of the conductive zinc oxide of present embodiment preparation is as shown in table 1.
Embodiment 8
10.567kg ZnSO
47H
2O and 0.226kg In (NO
3)
3(adding proportion of In is the 2.0mol% of integral molar quantity) is dissolved in and is mixed with mixing salt solution A in 25 premium on currency, and additive method is with embodiment 5.
The final measurement result of powder is: volume specific resistance is 8.3 * 10
-2Ω cm, whiteness value is 78, particle mean size is about 15nm-35nm.The performance of the conductive zinc oxide of present embodiment preparation is as shown in table 1.
The performance of the performance measurement result of the conductive zinc oxide of table 1 expression embodiment 1-8 preparation and the conductive zinc oxide of existing method preparation relatively.
The location parameter table of the various powders of table 1
| Sample number | Volume specific resistance (Ω cm) | Whiteness value (L) | Particle mean size (nm) |
| Vapor phase process sample (Japan) | ????1.8×10 -1 | ????78 | ????200-500 |
| The plasma method sample | ????8.0×10 -1 | ????70 | ????30-70 |
| Embodiment 1 | ????4.5×10 -1 | ????88 | ????80-150 |
| Embodiment 2 | ????2.5×10 -2 | ????81 | ????15-40 |
| Embodiment 3 | ????5.5×10 -2 | ????85 | ????10-30 |
| Embodiment 4 | ????5.4×10 1 | ????86 | ????60-100 |
| Embodiment 5 | ????5.0×10 -3 | ????70 | ????15-40 |
| Embodiment 6 | ????5.0×10 -1 | ????80 | ????15-40 |
| Embodiment 7 | ????3.2×10 -1 | ????82 | ????10-35 |
| Embodiment 8 | ????8.3×10 -2 | ????78 | ????15-35 |
Claims (5)
1. a method for preparing the super fine zinc oxide powder with high conductivity comprises the steps:
(1) at first synthetic zinc subcarbonate presoma: the soluble salt of zinc and doped element is mixed with mixing solutions, and concentration is 0.5mol/L-5.0mol/L, and the interpolation molar weight of doped element is the 0.1-10.0% of zinc and doped element integral molar quantity;
(2) will be as the yellow soda ash of precipitation agent, the mixing salt solution of preparation is added drop-wise in the water simultaneously in sodium bicarbonate or ammonium bicarbonate soln and the step (1), the concentration of precipitation agent is 0.5mol/L-4.0mol/L, keeping the temperature of reaction system in the dropping process is 40 ℃-75 ℃, the pH value is controlled in the 7.0-7.5 scope, apply violent stirring simultaneously, generate as even adulterated white zinc subcarbonate precipitation, the sodium hydroxide solution of the additional 0.5-4.0mol/L of dropping or ammonia soln are to keep the constant of pH value after precipitant solution drips again, and the mixing salt solution of preparing up to step (1) is added dropwise to complete; Ageing 0-4 hour;
(3) the precipitate and separate after drying that step (2) is made, the powder of gained is calcined under the mixed atmosphere of hydrogen and argon gas, and calcining temperature is 400 ℃-700 ℃, and constant temperature time is 0-4 hour, can obtain final conductive zinc oxide powder after the calcining.
2. have the method for the super fine zinc oxide powder of high conductivity by the described preparation of claim 1, it is characterized in that: the soluble salt of described doped element comprises the soluble salt of aluminium, gallium, indium, yttrium, scandium, tin, germanium, silicon.
3. have the method for the super fine zinc oxide powder of high conductivity by the described preparation of claim 1, it is characterized in that: the soluble salt of described zinc comprises: zinc nitrate, zinc chloride or zinc sulfate, the purity of salt is at least technical grade.
4. the coprecipitation method that has the super fine zinc oxide powder of high conductivity by claim 1 or 2 described preparations, it is characterized in that: the nitric acid soluble salt of described doped element, muriate soluble salt or sulfuric acid soluble salt, the purity of salt is at least technical grade.
5. have the coprecipitation method of the super fine zinc oxide powder of high conductivity by the described preparation of claim 1, it is characterized in that: the mixed gas of described step (3) comprises hydrogen and argon gas, and wherein the volume ratio of hydrogen is 0.5%-100%.
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