CN107473737B - Composite zirconia powder for solid oxide fuel cell and preparation method thereof - Google Patents
Composite zirconia powder for solid oxide fuel cell and preparation method thereof Download PDFInfo
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 239000000843 powder Substances 0.000 title claims abstract description 39
- 239000000446 fuel Substances 0.000 title claims abstract description 38
- 239000007787 solid Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 28
- 239000000654 additive Substances 0.000 claims abstract description 19
- 230000000996 additive effect Effects 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 17
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 13
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 8
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 7
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 7
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000004576 sand Substances 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002001 electrolyte material Substances 0.000 abstract description 12
- 239000003792 electrolyte Substances 0.000 abstract description 9
- 238000005452 bending Methods 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 7
- 238000005054 agglomeration Methods 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 238000010923 batch production Methods 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract 1
- 239000002002 slurry Substances 0.000 description 12
- 238000005245 sintering Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 5
- 238000010248 power generation Methods 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
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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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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
The invention relates toThe composite zirconia powder for solid oxide fuel cell and its preparation process includes adding composite oxide additive and PEG dispersant into zirconium oxychloride aqua, with the composite oxide additive being Al2O3、TiO2、CeO2、Bi2O3、Li2O, wherein each component of the composite oxide additive accounts for 0.2-5 wt% of the total system, and the solid oxide fuel cell electrolyte sheet prepared from the composite zirconia powder is prepared through the steps of precipitation, aging, filtering, washing and the like, wherein the conductivity of the solid oxide fuel cell electrolyte sheet is 0.37s/cm at 800 ℃, and the bending strength Kf is>580MPa, not only can meet the application of serving as a high-performance electrolyte material in a solid oxide fuel cell, but also has the characteristics of less agglomeration, small particle size, uniform particle size distribution, high powder activity, safety and convenience in operation and the like, and is suitable for industrial batch production.
Description
Technical Field
The invention belongs to the field of production methods of solid oxide fuel cells, and particularly relates to composite zirconia powder for a solid oxide fuel cell and a preparation method thereof.
Background
Solid Oxide Fuel Cells (SOFC), which are efficient and clean energy conversion systems, can directly convert chemical energy of fuel gas and oxidizing gas into electric energy, have the advantages of high power generation efficiency, high response speed, small volume, low pollution, easy assembly and maintenance and the like, and are known as an efficient, energy-saving and environment-friendly power generation technology following hydroelectric power generation, thermal power generation and nuclear power generation. The development and application of SOFC have become a research hotspot in the field of new materials and new energy.
The electrolyte material is a key component of the SOFC, at present, most SOFCs use 5-10 mol% yttria stabilized zirconia as a solid electrolyte, but the conductivity of the solid electrolyte is low, and the mechanical property is general, so that the further development of the SOFC is restricted, therefore, a new electrolyte material with higher conductivity, stronger mechanical property and good ageing resistance is found, and the method is a key for developing a high-performance solid oxide fuel cell.
The electrolyte material prepared by zirconia using scandium oxide as a stabilizer has higher conductivity, but the mechanical property is reduced, and the research results at present show that the comprehensive performance of the electrolyte material prepared by zirconia using yttrium oxide or scandium oxide or one oxide as a stabilizer is not excellent, the research on the preparation process of zirconia doped with various oxides is carried out, but the research has not made a major breakthrough, and the conductivity of the zirconia electrolyte material prepared by the relatively better process technology is about 0.12S/cm (at 800 ℃), and the bending strength is about 500 MPa.
The intensive research on the crystal structure of the zirconia is helpful for searching more suitable oxides for doping, and research shows that in a zirconia system, due to the influence of lattice stress and steric effect, Zr is replaced4+The closer the cation radius is to it, the higher its conductivity. S.P.S.Badwal et al by 9 mol% (Sc)2O3-Y2O3)-ZrO2Adding Al to the system2O3It was found that Al2O3Can purify grain boundary, reduce grain boundary resistance and increase the ZrO2Mechanical strength of the base system, but addition of Al2O3Then, ZrO2The conductivity of the system decreases faster with increasing quench time. Chakrapani Varanasi et Al investigated the doping of 6ScSZ with Al2O3As a result, it was found that Al2O3The addition of (2) increased the conductivity of 6ScSZ, doping with 30 wt.% Al2O3The conductivity of 6ScSZ at 850 ℃ was 0.12S/cm, which is higher than that of the alloy without Al2O3The conductivity is improved by about 20 percent. Bi has been studied by Masanio Hirano et al2O3The properties of the doped 10ScSZ comprise sintering characteristic, microstructure, crystal transformation, conductivity and mechanical strengthMechanical properties and the like, and research results show that: addition of 1 mol% Bi to 10ScSZ2O3Can effectively prevent the crystal form transformation of the zirconia and well reserve the cubic crystal form (high conductivity crystal form) of the zirconia, so 1mol percent of Bi is added2O3After that, the conductivity of 10ScSZ was improved.
In general, a great deal of research is done on zirconia for solid oxide fuel cells at home and abroad at present, mainly comprising YSZ and ScSZ, and stabilized zirconia doped with a third phase, some preparation methods are only limited to laboratory or small-scale preparation, and industrial production is difficult to form; zirconia powder prepared by some methods has the problems of serious agglomeration, difficult sintering and the like; electrolyte materials prepared from zirconia powder prepared by some methods cannot meet the requirements of high conductivity and strong mechanical property at the same time.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the composite zirconia powder for the solid oxide fuel cell and the preparation method thereof have the advantages of less agglomeration, small particle size, uniform particle size distribution, high powder activity, high conductivity and strong mechanical property.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of composite zirconia powder for a solid oxide fuel cell comprises the following steps:
step 1, preparing a zirconium oxychloride aqueous solution with the concentration of 0.5-1.5mol/L, and heating to 70 ℃; subjecting Sc to2O3、Y2O3Dissolving in 70 deg.C zirconium oxychloride water solution, and dissolving to obtain Sc2O3In an amount of 1 to 7 mol%, Y2O3The content of (A) is 1-7 mol%;
step 3, adding urea into the product obtained in the step 2 under stirring, wherein the urea accounts for 5-10 wt% of the total system, slowly adding ammonia water, and adjusting the pH value of the system to 8.5-9.5;
step 4, aging the product obtained in the step 3 for 2-6h, and adding the aged product into a reaction kettle for hydrothermal reaction at the temperature of 200-;
step 5, filtering and washing the product obtained in the step 4, washing the product by deionized water for circulation washing until the detected conductivity of the washing water is less than 150 mus/cm, finally washing the product by ethanol for 2 times, and drying the filter cake at 105 ℃ for 2-12 h;
step 6, calcining the dried lump material at 650-1000 ℃ for 1-6 h;
and 7, crushing the calcined lump materials through a vibration mill, performing superfine grinding by using a sand mill until the median particle size D50 is less than 0.2 mu m, and finally performing spray granulation to obtain the composite zirconia powder for the solid oxide fuel cell.
The invention also provides the composite zirconia powder for the solid oxide fuel cell, which is prepared by the preparation method of the composite zirconia powder for the solid oxide fuel cell.
The invention has the beneficial effects that: the solid oxide fuel cell electrolyte sheet prepared from the composite zirconia powder prepared by the method has the conductivity of 0.37s/cm at 800 ℃, the bending strength Kf is more than 580MPa, the application of the solid oxide fuel cell electrolyte sheet as a high-performance electrolyte material can be met, and the preparation method has the characteristics of low energy consumption, less agglomeration, small particle size, uniform particle size distribution, high powder activity, safe and convenient operation and the like, and is suitable for industrial batch production.
Drawings
FIG. 1 is a particle size distribution diagram of composite zirconia powder of example 2 according to an embodiment of the present invention.
Detailed Description
In order to explain technical contents, achieved objects, and effects of the present invention in detail, the following description is made with reference to the accompanying drawings in combination with the embodiments.
The most key concept of the invention is as follows: after the composite oxide additive is added into the zirconium oxychloride aqueous solution, the prepared composite zirconia powder for the solid oxide fuel cell has the advantages of low energy consumption, less agglomeration, small particle size, uniform particle size distribution, high powder activity, high conductivity and strong mechanical property.
A preparation method of composite zirconia powder for a solid oxide fuel cell comprises the following steps:
step 1, preparing a zirconium oxychloride aqueous solution with the concentration of 0.5-1.5mol/L, and heating to 70 ℃; subjecting Sc to2O3、Y2O3Dissolving in 70 deg.C zirconium oxychloride water solution, and dissolving to obtain Sc2O3In an amount of 1 to 7 mol%, Y2O3The content of (A) is 1-7 mol%;
step 3, adding urea into the product obtained in the step 2 under stirring, wherein the urea accounts for 5-10 wt% of the total system, slowly adding ammonia water, and adjusting the pH value of the system to 8.5-9.5;
step 4, aging the product obtained in the step 3 for 2-6h, and adding the aged product into a reaction kettle for hydrothermal reaction at the temperature of 200-;
step 5, filtering and washing the product obtained in the step 4, washing the product by deionized water for circulation washing until the detected conductivity of the washing water is less than 150 mus/cm, finally washing the product by ethanol for 2 times, and drying the filter cake at 105 ℃ for 2-12 h;
step 6, calcining the dried lump material at 650-1000 ℃ for 1-6 h;
and 7, crushing the calcined lump materials through a vibration mill, performing superfine grinding by using a sand mill until the median particle size D50 is less than 0.2 mu m, and finally performing spray granulation to obtain the composite zirconia powder for the solid oxide fuel cell.
The invention also provides the composite zirconia powder for the solid oxide fuel cell, which is prepared by the preparation method of the composite zirconia powder for the solid oxide fuel cell.
From the above description, the beneficial effects of the present invention are: the solid oxide fuel cell electrolyte sheet prepared from the composite zirconia powder prepared by the method has the conductivity of 0.37s/cm at 800 ℃, the bending strength Kf is more than 580MPa, the application of the solid oxide fuel cell electrolyte sheet as a high-performance electrolyte material can be met, and the preparation method has the characteristics of low energy consumption, less agglomeration, small particle size, uniform particle size distribution, high powder activity, safe and convenient operation and the like, and is suitable for industrial batch production.
Example 1
A preparation method of composite zirconia powder for a solid oxide fuel cell comprises the following specific steps:
(1) weighing zirconium oxychloride, adding deionized water to prepare an aqueous solution with the concentration of 1mol/L, heating to 70 ℃, and adding Sc2O3、Y2O3Dissolved in a zirconium oxychloride solution, the Sc2O3Is 3 mol%, the Y2O3The content of (2) is 7 mol%, a composite oxide additive is added, and the composite oxide additive is formed by Al2O3、TiO2、CeO2、Bi2O3、Li2O accounts for 4 wt% of the total system, wherein Al is2O3The addition was 1.5 wt.%, TiO2The addition amount was 0.5 wt.%, CeO2Added in an amount of 0.5 wt.%, Bi2O3Addition of 1 wt.%, Li2The addition amount of O is 0.5 wt.%, and 0.2 wt.% of PEG dispersant is added;
(2) slowly adding urea with the mass fraction of 5 wt.% of the total system under stirring, slowly adding ammonia water, hydrolyzing and precipitating, and adjusting the pH value of the slurry system to 8.5;
(3) aging the obtained slurry for 2h, and adding the aged slurry into a reaction kettle to perform hydrothermal reaction for 18h at 230 ℃;
(4) filtering and washing the slurry after hydrothermal treatment, washing with deionized water for circulation till the conductivity is less than 150 mus/cm when the washing water is removed, finally washing with ethanol for 2 times, and drying the filter cake at 105 ℃ for 6 h.
(5) The dried cake was calcined at 650 ℃ for 3 h.
(6) After the calcined lump materials are crushed by a vibration mill, the lump materials are subjected to superfine grinding by a sand mill until the median particle diameter D50 is 0.15 mu m and the specific surface area is 16m2(g), finally carrying out spray granulation to obtain the composite zirconia powder suitable for the electrolyte material of the solid oxide fuel cell, wherein the sintering temperature is 1280 ℃, and the sintering density is 5.9g/cm3. The electrolyte sheet of solid oxide fuel cell prepared from the composite zirconia powder prepared by the invention has the conductivity of 0.31s/cm at 800 ℃, and the bending strength Kf>530MPa。
Example 2
A preparation method of composite zirconia powder for a solid oxide fuel cell comprises the following specific steps:
(1) weighing zirconium oxychloride, adding deionized water to prepare an aqueous solution with the concentration of 1mol/L, heating to 70 ℃, and adding Sc2O3、Y2O3Dissolved in a zirconium oxychloride solution, the Sc2O3Is 5 mol%, the Y2O3The content of (2) is 5 mol%, a composite oxide additive is added, and the composite oxide additive is formed by Al2O3、TiO2、CeO2、Bi2O3、Li2O accounts for 5 wt% of the total system, wherein Al is2O3The addition was 2 wt.%, TiO2The addition was 1 wt.%, CeO2Added in an amount of 0.5 wt.%, Bi2O3Addition amount was 0.5 wt.%, Li2The addition amount of O is 1 wt.%, and 0.3 wt.% of PEG dispersant is added;
(2) slowly adding urea with the mass fraction of 7 wt.% in the total system under stirring, slowly adding ammonia water, hydrolyzing and precipitating, and adjusting the pH value of the slurry system to 9;
(3) aging the obtained slurry for 3h, adding the aged slurry into a reaction kettle, and carrying out hydrothermal reaction for 12h at 240 ℃;
(4) filtering and washing the slurry after hydrothermal treatment, washing with deionized water for circulation till the conductivity is less than 150 mus/cm when the washing water is removed, finally washing with ethanol for 2 times, and drying the filter cake at 105 ℃ for 7 h.
(5) The dried blocks were calcined at 700 ℃ for 3 h.
(6) Pulverizing calcined lump material by vibration mill, and grinding with sand mill to obtain powder with median particle diameter D50 of 0.098 μm, particle size distribution shown in FIG. 1, and specific surface area of 18m2(g), finally spray granulating to obtain the composite zirconia powder suitable for the electrolyte material of the solid oxide fuel cell, wherein the sintering temperature is 1260 ℃, and the sintering density is 6.0g/cm3. The electrolyte sheet of solid oxide fuel cell prepared from the composite zirconia powder prepared by the invention has the conductivity of 0.37s/cm at 800 ℃, and the bending strength Kf>580MPa。
Example 3
A preparation method of composite zirconia powder for a solid oxide fuel cell comprises the following specific steps:
(1) weighing zirconium oxychloride, adding deionized water to prepare an aqueous solution with the concentration of 1mol/L, heating to 70 ℃, and adding Sc2O3、Y2O3Dissolved in a zirconium oxychloride solution, the Sc2O3Is 7 mol%, the Y2O3The content of (2) is 3 mol%, a composite oxide additive is added, and the composite oxide additive is formed by Al2O3、TiO2、CeO2、Bi2O3、Li2O accounts for 1 wt% of the total system, wherein Al accounts for2O3The addition was 0.2 wt.%, TiO2The addition amount was 0.2 wt.%, CeO2Added in an amount of 0.2 wt.%, Bi2O3Addition amount was 0.2 wt.%, Li2The addition amount of O is 0.2 wt.%, and 0.3 wt.% of PEG dispersant is added;
(2) slowly adding urea with the mass fraction of 5 wt.% of the total system under stirring, slowly adding ammonia water, hydrolyzing and precipitating, and adjusting the pH value of the slurry system to 9.5;
(3) aging the obtained slurry for 2h, and adding the aged slurry into a reaction kettle to perform hydrothermal reaction for 6h at 240 ℃;
(4) filtering and washing the slurry after hydrothermal treatment, washing with deionized water for circulation till the conductivity is less than 150 mus/cm when the washing water is removed, finally washing with ethanol for 2 times, and drying the filter cake at 105 ℃ for 8 h.
(5) The dried blocks were calcined at 800 ℃ for 2 h.
(6) After the calcined lump materials are crushed by a vibration mill, the lump materials are subjected to superfine grinding by a sand mill until the median particle diameter D50 is 0.18 mu m and the specific surface area is 14m2(g), finally carrying out spray granulation to obtain the composite zirconia powder suitable for the electrolyte material of the solid oxide fuel cell, wherein the sintering temperature is 1300 ℃, and the sintering density is 5.8g/cm3. The electrolyte sheet of solid oxide fuel cell prepared from the composite zirconia powder prepared by the invention has the conductivity of 0.35s/cm at 800 ℃, and the bending strength Kf>515MPa。
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent changes made by using the contents of the present specification and the drawings, or applied directly or indirectly to the related technical fields, are included in the scope of the present invention.
Claims (2)
1. A preparation method of composite zirconia powder for a solid oxide fuel cell is characterized by comprising the following steps: the method comprises the following steps:
step 1, preparing a zirconium oxychloride aqueous solution with the concentration of 0.5-1.5mol/L, and heating to 70 ℃; subjecting Sc to2O3、Y2O3Dissolving in 70 deg.C zirconium oxychloride water solution, and dissolving to obtain Sc2O3In an amount of 1 to 7 mol%, Y2O3The content of (A) is 1-7 mol%;
step 2, adding the solution obtained in the step 1Adding a composite oxide additive and a PEG dispersing agent, wherein the composite oxide additive is prepared from Al2O3、TiO2、CeO2、Bi2O3、Li2O, wherein each component of the composite oxide additive accounts for 0.2-5 wt% of the total system, and the PEG dispersant accounts for 0.2-0.5 wt% of the total system;
step 3, adding urea into the product obtained in the step 2 under stirring, wherein the urea accounts for 5-10 wt% of the total system, slowly adding ammonia water, and adjusting the pH value of the system to 8.5-9.5;
step 4, aging the product obtained in the step 3 for 2-6h, and adding the aged product into a reaction kettle for hydrothermal reaction at the temperature of 200-;
step 5, filtering and washing the product obtained in the step 4, washing the product by deionized water for circulation washing until the detected conductivity of the washing water is less than 150 mus/cm, finally washing the product by ethanol for 2 times, and drying the filter cake at 105 ℃ for 2-12 h;
step 6, calcining the dried lump material at 650-1000 ℃ for 1-6 h;
and 7, crushing the calcined lump materials through a vibration mill, performing superfine grinding by using a sand mill until the median particle size D50 is less than 0.2 mu m, and finally performing spray granulation to obtain the composite zirconia powder for the solid oxide fuel cell.
2. A composite zirconia powder for a solid oxide fuel cell produced by the method for producing a composite zirconia powder for a solid oxide fuel cell according to claim 1.
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