CN111592038A - Preparation method of scandia-stabilized zirconia nano-powder - Google Patents
Preparation method of scandia-stabilized zirconia nano-powder Download PDFInfo
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- 229910002076 stabilized zirconia Inorganic materials 0.000 title claims abstract description 33
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 241000968352 Scandia <hydrozoan> Species 0.000 claims abstract description 13
- HJGMWXTVGKLUAQ-UHFFFAOYSA-N oxygen(2-);scandium(3+) Chemical compound [O-2].[O-2].[O-2].[Sc+3].[Sc+3] HJGMWXTVGKLUAQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000004202 carbamide Substances 0.000 claims abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 56
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000002776 aggregation Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000004220 aggregation Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 3
- 238000010345 tape casting Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- -1 salt zirconium oxychloride Chemical class 0.000 abstract description 2
- 229910018057 ScCl3 Inorganic materials 0.000 abstract 1
- 229910006213 ZrOCl2 Inorganic materials 0.000 abstract 1
- 239000000413 hydrolysate Substances 0.000 abstract 1
- 238000010335 hydrothermal treatment Methods 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- 239000003381 stabilizer Substances 0.000 abstract 1
- 238000000975 co-precipitation Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052706 scandium Inorganic materials 0.000 description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- XPFAJCSMHOQBQB-UHFFFAOYSA-N 2-aminoacetic acid;nitric acid Chemical compound O[N+]([O-])=O.NCC(O)=O XPFAJCSMHOQBQB-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
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Abstract
The invention relates to a preparation method of fully stable cubic phase scandia-stabilized zirconia nano-powder, which comprises a precursor mother salt zirconium oxychloride and a stabilizer scandia, wherein the doping amount of the scandia accounts for 8-10 mol%. The preparation method comprises low-temperature hydrolysis reaction and high-temperature hydrothermal reaction, and firstly, the precursor mother salt solution ZrOCl2(ScCl3Urea) is subjected to low-temperature hydrolysis treatment in a reaction kettle, and then the hydrolysate is subjected to hydrothermal treatment at the temperature of 160-200 ℃. The product has the characteristics of small particle size, concentrated particle size distribution, low sintering temperature, moderate specific surface area and the like, can be suitable for the conventional tape casting process of SOFC, has simple production process, and is easy to realize industrialized large-scale production.
Description
Technical Field
The invention relates to a preparation method of cubic phase scandium oxide stabilized zirconia nano powder.
Background
Solid Oxide Fuel Cells (SOFC) are a novel electrochemical power generation device. Because of its advantages of environmental friendliness and high energy conversion rate, it is receiving more and more attention.
At present, the cityThe electrolyte used in most commercially available SOFCs is Yttria Stabilized Zirconia (YSZ) at 6-10 mol. However, the conventional SOFC device using YSZ as electrolyte has disadvantages such as high operation temperature (800-1000 ℃), difficult packaging, poor interface stability, poor conductivity, etc. In the related experimental reports, the scandia-stabilized zirconia system has higher ionic conductivity and low working temperature (600-800 ℃) in the stabilized zirconia system. Wherein the ingredient is (Sc)2O3)0.08(ZrO2)0.92(8ScZr) has the highest conductivity among the zirconium-based oxygen ion conductors.
The cubic-phase scandia-stabilized zirconia is an excellent oxygen ion conductor, has excellent oxygen ion conductivity under the condition of medium temperature (600-800 ℃), has excellent stability at the temperature, and is the most promising SOFC electrolyte at present. Therefore, the synthesis of zirconia with stable cubic phase is of great significance.
There are many methods for preparing scandia-stabilized zirconia at present, and a coprecipitation method, a sol-gel method, a solid phase method, a thermal decomposition method, a spray thermal decomposition method, and a hydrothermal method have been reported. Lee et al prepared 8 mol% scandium stabilized zirconia powder by glycine-nitrate method, sintered at 1600 ℃ for 6 hours to form pure cubic phase or tetragonal sintered body with conductivity of 0.15S/cm (800 ℃). Anshenli and the like synthesized scandia-stabilized zirconia (9 mol% Sc) by a coprecipitation method2O3) And (3) powder. Mizutani Yasunobu and the like take scandium powder, zirconium salt and nitric acid as raw materials, and prepare scandia-stabilized zirconia powder by respectively adopting a coprecipitation method and a sol-gel method, wherein the powder can be finally prepared into an electrode plate product only through isostatic pressing and under the harsh condition of sintering at the high temperature of 1500-1700 ℃. Y.Mizutani et al ZrO (NO)3)2And Sc with a purity of 99.9%2O38ScSZ powder is prepared by a sol-gel method, and the powder is hot pressed and sintered at the temperature of 1600-1700 ℃ (the pressure is 2000Kg/cm2) for 5-15 hours, and then the conductivity is measured to be 0.38S/cm (1000 ℃).
In summary, the existing preparation techniques such as sol-gel and coprecipitation are difficult to implement industrial mass production, and the methods such as coprecipitation can rapidly increase local concentration due to the addition of a precipitant (mineralizer), which results in hard agglomeration and uneven doping of the prepared powder. Moreover, the powder prepared by the method has the defects of over-high sintering temperature and harsh forming conditions, and is not easy to use in industrial large-scale production.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide the preparation method of the scandia-stabilized zirconia nano-powder used in the solid fuel cell, the prepared product has the characteristics of small particle size, concentrated particle size distribution and moderate specific surface area, can be suitable for the existing tape-casting process of the SOFC, and has the advantages of simple and safe production process, low equipment requirement, high yield, low raw material cost and easy realization of industrial production.
The technical scheme adopted for realizing the purpose is as follows:
a preparation method of scandia-stabilized zirconia nano-powder comprises the following steps:
(1) adding hydrochloric acid into the scandium oxide powder, and heating until the scandium oxide is dissolved to obtain a scandium oxide solution;
(2) mixing a zirconium oxychloride solution and a scandium oxide solution, and performing ultrasonic stirring to uniformly mix the zirconium oxychloride solution and the scandium oxide solution to obtain a precursor clear solution;
(3) adding urea serving as a mineralizer into the clear precursor solution obtained in the step (2), simultaneously adding CTAB or a mixture of CTAB and PEG400 serving as a dispersing agent, and ultrasonically dissolving the mixture in a mixed solution of deionized water and absolute ethyl alcohol to obtain a hydrothermal clear precursor solution;
(4) hydrolyzing the clear solution of the hydrothermal precursor obtained in the step (3) at 80 ℃ for 12-24 hours;
(5) after the low-temperature hydrolysis in the step (4) is finished, immediately adjusting the temperature to 160-200 ℃, carrying out high-temperature hydrothermal for 36-64 hours, and standing until natural cooling to obtain a white turbid solution;
(6) and centrifuging the white turbid solution, cleaning for multiple times to obtain a white precipitate, drying and grinding to obtain the scandia-stabilized zirconia nano powder.
Preferably, in the scandia-stabilized zirconia nanopowder, the content of scandia is 8-10 mol%.
Preferably, the molar ratio of scandium oxide to HCl in the step (1) is more than 1:6, the concentration of hydrochloric acid is 1-10 mol/L, and the temperature for heating and dissolving is more than 100 ℃.
Preferably, the zirconium oxychloride solution and the scandium oxide solution in the step (2) are mixed according to the doping amount of scandium oxide of 8-10 mol%, and the solute concentration in the precursor clear solution prepared in the step (2) is 0.2-0.6 mol/L.
Preferably, in the mixed solution of the deionized water and the absolute ethyl alcohol in the step (3), the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 0.5-1: 2.
Preferably, the molar concentration ratio of the urea in the step (3) to the solute in the precursor clear solution is 1: 1-4: 1.
Preferably, the addition amount of the dispersing agent in the step (3) accounts for 1-5 wt% of the total mass of the solute in the precursor clear solution.
Preferably, the solution used for washing in the step (6) is deionized water and absolute ethyl alcohol.
The size of the twice-agglomerated particle diameter of the scandia-stabilized zirconia nano-powder prepared by the preparation method is 0.2-1 um.
Compared with the prior art, the invention has the following advantages.
(1) The invention adopts urea as a mineralizer, combines a uniform coprecipitation method and a hydrothermal method, and uniformly releases ammonia water during the heating process by urea hydrolysis, thereby avoiding the uneven precipitation caused by adding other mineralizers (ammonia water/sodium hydroxide solution and the like) from the outside in the traditional process, ensuring that the particle size of the product powder is more uniform and large-scale agglomeration is not easily formed.
(2) The invention is in a clear solution state before low-temperature hydrolysis and high-temperature hydrothermal, is easy to transfer into a reaction kettle container, does not cause accelerated damage to equipment or reduction of yield due to raw material residue, and saves certain cost.
(3) The invention needs simple equipment and does not need to additionally customize a special hydrothermal reaction kettle which can additionally feed materials in the hydrothermal process.
(4) The powder has the characteristics of small particle size and concentrated particle size distribution, can be suitable for the existing tape-casting process of SOFC, has simple and safe production process, lower cost and low requirement on equipment, and is easy to realize industrialized mass production.
Drawings
FIG. 1: the process flow diagram of the invention;
FIG. 2: XRD patterns of scandia-stabilized zirconia nanopowders of examples 1 to 4.
Detailed Description
For better illustrating the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific embodiments below:
example 1:
one embodiment of the method for preparing the scandia-stabilized zirconia nanopowder of the present invention comprises the steps of:
(1) dissolving: scandium oxide powder is weighed in a beaker, hydrochloric acid with the concentration of 4mol/L (the molar ratio of scandium oxide to HCl is more than 1:6) is added in the beaker, and the beaker is heated at the temperature of more than 100 ℃ until scandium oxide is dissolved, so that scandium oxide solution with the concentration of 2mol/L is obtained.
(2) Mixing: preparing a zirconium oxychloride solution with the concentration of 2mol/L, respectively taking 20.7mL of the zirconium oxychloride solution and 3.6mL of the scandium oxide solution to meet the condition that the doping amount of the scandium oxide is 8 mol%, wherein the concentration of solute in the mixed solution is 0.6mol/L, and ultrasonically stirring to uniformly mix the solutions to obtain a precursor clear solution.
(3) And (3) adding urea with the molar concentration ratio of 1: 1-4: 1 to the solute in the precursor clear solution obtained in the step (2) as a mineralizer, simultaneously adding 1-5 wt% (the addition amount of the dispersing agent accounts for the total mass of the solute in the precursor clear solution) of CTAB or a mixture of CTAB and PEG400 as a dispersing agent, and ultrasonically dissolving the mixture in a mixed solution of deionized water and absolute ethyl alcohol (the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 0.5-1: 2) to obtain a hydrothermal precursor clear solution with the total volume of 75-80 mL.
(4) Low-temperature hydrolysis: and (4) transferring the clear solution of the hydrothermal precursor obtained in the step (3) into a 100 ml tetrachloroethylene lining, and putting the lining into a reaction kettle to react for 24 hours at the temperature of 80 ℃.
(5) High-temperature hydrothermal: and (4) after the step (4) is finished, immediately raising the temperature to 160-200 ℃ and reacting for 36-64 hours. And after the reaction kettle is naturally cooled, taking out the white turbid solution in the tetrafluoroethylene liner.
(6) Centrifugal cleaning: and (4) placing the white turbid solution obtained in the step (5) in a centrifuge, and respectively carrying out 4 times of centrifugal cleaning by using deionized water and absolute ethyl alcohol until chloride ions cannot be detected in the cleaning solution.
(7) Drying and grinding: drying the white powder obtained after centrifugal cleaning in an oven for 12 hours, and simply grinding to obtain white powder, namely the scandia-stabilized zirconia nano powder, with the particle size of D50: 0.5 um. The secondary agglomeration particle size of the scandia-stabilized zirconia nano-powder obtained in the embodiment is 0.2-1 um.
Example 2: on the basis of example 1, the addition amounts of the zirconium oxychloride solution and the scandia solution in step 2 were changed to 13.8mL and 2.4mL, respectively, so that the solute concentration in the mixed solution was changed to 0.4mol/L while the scandia doping ratio was kept constant at 8 mol%. The remaining conditions and steps were not changed, and results consistent with example 1 were obtained.
Example 3: on the basis of example 1, the addition amounts of the zirconium oxychloride solution and the scandia solution in step 2 were changed to 6.9mL and 1.2mL, respectively, so that the solute concentration in the mixed solution was changed to 0.2mol/L while the scandia doping ratio was kept unchanged at 8 mol%. The remaining conditions and steps were not changed, and results consistent with example 1 were obtained.
Example 4: on the basis of example 1, the addition amounts of the zirconium oxychloride solution and the scandia solution in step 2 were changed to 20.25mL and 4.5mL, respectively, so that the doping ratio of scandia was changed to 10 mol% while the solute concentration in the mixed solution was changed to 0.6mol/L, and the other conditions and steps were not changed, thereby obtaining a result consistent with example 1.
FIG. 2 is an XRD pattern of a scandia-stabilized zirconia nanopowder obtained in examples 1 to 4. It can be seen from the figure that with the method of the present invention, the product can still maintain the crystal form of the cubic phase with the increase of the concentration of the reactant and the increase of the doping amount of scandium element. Thus, the invention is suitable for industrial production.
Claims (9)
1. A preparation method of scandia-stabilized zirconia nano-powder is characterized by comprising the following steps:
(1) adding hydrochloric acid into the scandium oxide powder, and heating until the scandium oxide is dissolved to obtain a scandium oxide solution;
(2) mixing a zirconium oxychloride solution and a scandium oxide solution, and performing ultrasonic stirring to uniformly mix the zirconium oxychloride solution and the scandium oxide solution to obtain a precursor clear solution;
(3) adding urea serving as a mineralizer into the clear precursor solution obtained in the step (2), simultaneously adding CTAB or a mixture of CTAB and PEG400 serving as a dispersing agent, and ultrasonically dissolving the mixture in a mixed solution of deionized water and absolute ethyl alcohol to obtain a hydrothermal clear precursor solution;
(4) hydrolyzing the clear solution of the hydrothermal precursor obtained in the step (3) at 80 ℃ for 12-24 hours;
(5) after the low-temperature hydrolysis in the step (4) is finished, immediately adjusting the temperature to 160-200 ℃, carrying out high-temperature hydrothermal for 36-64 hours, and standing until natural cooling to obtain a white turbid solution;
(6) and centrifuging the white turbid solution, cleaning for multiple times to obtain a white precipitate, drying and grinding to obtain the scandia-stabilized zirconia nano powder.
2. The method for producing a scandia-stabilized zirconia nanopowder according to claim 1, wherein the scandia content in the scandia-stabilized zirconia nanopowder is 8 to 10 mol%.
3. The method for preparing scandia-stabilized zirconia nanopowder according to claim 1, wherein the molar ratio of scandia to HCl in the step (1) is greater than 1:6, the concentration of hydrochloric acid is 1-10 mol/L, and the temperature for heating and dissolving is greater than 100 ℃.
4. The method for preparing the scandia-stabilized zirconia nanopowder according to claim 1, wherein the zirconium oxychloride solution and the scandia solution in the step (2) are mixed according to the doping amount of scandia being 8-10 mol%, and the solute concentration in the precursor clarified solution prepared in the step (2) is 0.2-0.6 mol/L.
5. The method for preparing scandia-stabilized zirconia nanopowder according to claim 1, wherein in the mixed solution of deionized water and absolute ethyl alcohol in the step (3), the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 0.5-1: 2.
6. The method for preparing the scandia-stabilized zirconia nanopowder according to claim 1, wherein the molar concentration ratio of the urea in the step (3) to the solute in the precursor clarified solution is 1: 1-4: 1.
7. The method for preparing the scandia-stabilized zirconia nanopowder according to claim 1, wherein the addition amount of the dispersant in the step (3) accounts for 1-5 wt% of the total mass of the solute in the precursor clear solution.
8. The method for preparing scandia-stabilized zirconia nanopowder according to claim 1, wherein the solution used for cleaning in step (6) is deionized water and absolute ethyl alcohol.
9. The method for preparing the scandia-stabilized zirconia nanopowder according to claim 1, wherein the secondary aggregation particle size of the scandia-stabilized zirconia nanopowder is 0.2-1 um.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114133240A (en) * | 2021-11-30 | 2022-03-04 | 广东先导稀材股份有限公司 | Method for preparing scandium-cerium-ytterbium-doped zirconia superfine powder by hydrolysis-hydrothermal method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1493519A (en) * | 2002-10-29 | 2004-05-05 | 北京有色金属研究总院 | Preparation of cerium zirconium composite oxide using coprecipitation-high pressure water heat combining method |
| CN1868894A (en) * | 2006-06-08 | 2006-11-29 | 中南大学 | Preparation method of stable zirconium oxide nanometer material doped with samarium oxide |
| CN110156076A (en) * | 2019-06-14 | 2019-08-23 | 南京赛诺特斯材料科技有限公司 | A kind of fiber stub, optical fiber sleeve nano zirconium oxide powder and its production technology |
-
2020
- 2020-04-14 CN CN202010288482.0A patent/CN111592038A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1493519A (en) * | 2002-10-29 | 2004-05-05 | 北京有色金属研究总院 | Preparation of cerium zirconium composite oxide using coprecipitation-high pressure water heat combining method |
| CN1868894A (en) * | 2006-06-08 | 2006-11-29 | 中南大学 | Preparation method of stable zirconium oxide nanometer material doped with samarium oxide |
| CN110156076A (en) * | 2019-06-14 | 2019-08-23 | 南京赛诺特斯材料科技有限公司 | A kind of fiber stub, optical fiber sleeve nano zirconium oxide powder and its production technology |
Non-Patent Citations (3)
| Title |
|---|
| GANG XU ET AL.: "Hydrothermal Synthesis of Weakly Agglomerated Nanocrystalline Scandia-Stabilized Zirconia", 《J. AM. CERAM. SOC.》 * |
| 吴其胜: "尿素为沉淀剂水热法制备稳定Y- Ce - ZrO2 纳米粉体", 《盐城工学院学报(自然科学版)》 * |
| 陶景超: ""稀土元素（铈、钪）与氧化锆材料形成的氧空位及其应用基础的研究"", 《万方数据知识服务平台》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114133240A (en) * | 2021-11-30 | 2022-03-04 | 广东先导稀材股份有限公司 | Method for preparing scandium-cerium-ytterbium-doped zirconia superfine powder by hydrolysis-hydrothermal method |
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