CN113511676A - Holmium oxide and scandium oxide composite stable zirconia, preparation method thereof and electrolyte material of solid oxide fuel cell - Google Patents
Holmium oxide and scandium oxide composite stable zirconia, preparation method thereof and electrolyte material of solid oxide fuel cell Download PDFInfo
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- CN113511676A CN113511676A CN202110459353.8A CN202110459353A CN113511676A CN 113511676 A CN113511676 A CN 113511676A CN 202110459353 A CN202110459353 A CN 202110459353A CN 113511676 A CN113511676 A CN 113511676A
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- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 title claims abstract description 64
- OWCYYNSBGXMRQN-UHFFFAOYSA-N holmium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ho+3].[Ho+3] OWCYYNSBGXMRQN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 239000007787 solid Substances 0.000 title claims abstract description 20
- 239000000446 fuel Substances 0.000 title claims abstract description 17
- 239000002001 electrolyte material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title abstract description 24
- 229910002076 stabilized zirconia Inorganic materials 0.000 claims abstract description 47
- -1 zirconium ions Chemical class 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 8
- 239000011268 mixed slurry Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 40
- 239000000843 powder Substances 0.000 claims description 24
- 238000000498 ball milling Methods 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000007921 spray Substances 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
- 239000000203 mixture Substances 0.000 claims description 5
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical group [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 238000011085 pressure filtration Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 210000003298 dental enamel Anatomy 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- LCTWRNOEZKTLGG-UHFFFAOYSA-K holmium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ho+3] LCTWRNOEZKTLGG-UHFFFAOYSA-K 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- LQPWUWOODZHKKW-UHFFFAOYSA-K scandium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Sc+3] LQPWUWOODZHKKW-UHFFFAOYSA-K 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 241000968352 Scandia <hydrozoan> Species 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940000635 beta-alanine Drugs 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000010987 cubic zirconia Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004689 octahydrates Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- HJGMWXTVGKLUAQ-UHFFFAOYSA-N oxygen(2-);scandium(3+) Chemical compound [O-2].[O-2].[O-2].[Sc+3].[Sc+3] HJGMWXTVGKLUAQ-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C01F17/10—Preparation or treatment, e.g. separation or purification
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- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/212—Scandium oxides or hydroxides
-
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- C01F17/224—Oxides or hydroxides of lanthanides
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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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Abstract
The invention relates to the technical field of electrolyte materials of solid oxide fuel cells, in particular to holmium oxide and scandium oxide composite stabilized zirconia, a preparation method thereof and an electrolyte material of a solid oxide fuel cell. The preparation method of the holmium oxide and scandium oxide composite stabilized zirconia comprises the following steps: heating a mixed aqueous solution of zirconium oxychloride, scandium oxide and holmium oxide, adjusting the pH value to obtain a mixed slurry, and then filtering, washing, drying, calcining and grinding; in the mixed aqueous solution, the molar ratio of zirconium ions to scandium ions to holmium ions is (92-93): 6-7): 1. The method is simple and feasible, and the obtained holmium oxide and scandium oxide composite stable zirconia has excellent ion conductivity.
Description
Technical Field
The invention relates to the technical field of electrolyte materials of solid oxide fuel cells, in particular to holmium oxide and scandium oxide composite stabilized zirconia, a preparation method thereof and an electrolyte material of a solid oxide fuel cell.
Background
The scandium oxide stabilized zirconia powder has the characteristics of small particle size, concentrated particle size distribution, high sintering activity and lower specific surface area, and can be widely applied to the existing tape casting method of the electrolyte substrate of the solid oxide fuel cell. In the prior art, the zirconia stabilized by yttria has lower conductivity and general mechanical property as a solid electrolyte, and further development of a solid oxide fuel cell is restricted.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of holmium oxide and scandium oxide composite stabilized zirconia, which is simple and feasible, and the obtained holmium oxide and scandium oxide composite stabilized zirconia has excellent ion conductivity.
The invention also aims to provide the holmium oxide and scandium oxide composite stabilized zirconia obtained by the preparation method of the holmium oxide and scandium oxide composite stabilized zirconia.
Another object of the present invention is to provide an electrolyte material for a solid oxide fuel cell, which is mainly prepared from the holmium oxide and scandium oxide composite stabilized zirconia as described above.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a preparation method of holmium oxide and scandium oxide composite stabilized zirconia comprises the following steps:
heating a mixed aqueous solution of zirconium oxychloride, scandium oxide and holmium oxide, adjusting the pH value to obtain a mixed slurry, and then filtering, washing, drying, calcining and grinding;
in the mixed aqueous solution, the molar ratio of zirconium ions to scandium ions to holmium ions is (92-93): 6-7): 1.
Preferably, the concentration of the zirconium oxychloride in the mixed aqueous solution is 0.02-0.6 mol/L.
Preferably, the heating temperature is 98-100 ℃, and the heating time is 96-120 h.
Preferably, ammonia water is used for adjusting the pH;
and adjusting the pH value of the heated solution to 7-8.
Preferably, the filtration adopts filter pressing and/or suction filtration;
washing until no chloride ion exists;
the drying temperature is 115-125 ℃, and the drying time is 20-25 h.
Preferably, the calcining temperature is 600-900 ℃, and the calcining time is 1.5-2.5 h.
Preferably, the grinding comprises: mixing the calcined material, a dispersing agent and water for grinding;
the dispersant is selected from ammonium citrate and/or triethanolamine;
the addition amount of the dispersing agent is 0.4-0.6% of the mass of the calcined material;
the mass ratio of the calcined material to the water used in the grinding process is (5-30) to (70-95);
the grinding is ball milling;
the ball milling time is 20-25 h.
The holmium oxide and scandium oxide composite stabilized zirconia is prepared by the preparation method of the holmium oxide and scandium oxide composite stabilized zirconia.
An electrolyte material of a solid oxide fuel cell is mainly prepared from the holmium oxide and scandium oxide composite stabilized zirconia.
Preferably, the electrolyte material of the solid oxide fuel cell is mainly obtained by performing spray granulation on a mixture of the holmium oxide and scandium oxide composite stabilized zirconia and a binder;
the addition amount of the binder is 0.4-0.6% of the mass of the holmium oxide and scandium oxide composite stabilized zirconia;
the binder is selected from PVA.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method of the holmium oxide and scandium oxide composite stable zirconia is simple and easy to implement, and the obtained holmium oxide and scandium oxide composite stable zirconia has excellent ion conductivity.
(2) The electrolyte material of the solid oxide fuel cell is mainly prepared from the holmium oxide and scandium oxide composite stabilized zirconia, and has excellent intra-crystal conductivity and grain boundary conductivity.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a transmission electron microscope morphology of a holmium oxide and scandium oxide composite stabilized zirconia powder obtained in example 1 of the present invention;
fig. 2 is a transmission electron microscope morphology diagram of the holmium oxide and scandium oxide composite stabilized zirconia powder obtained in example 2 of the present invention;
FIG. 3 is a scanning electron microscope topography of the powder obtained in example 3 of the present invention;
FIG. 4 is a crystal structure X-ray diffraction pattern of scandia-stabilized zirconia;
FIG. 5 is an X-ray diffraction diagram of the crystal structure of scandium oxide and holmium oxide composite stabilized zirconia powder;
FIG. 6 is a graph of grain conductivity;
FIG. 7 is a graph of grain boundary conductivity.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
A preparation method of holmium oxide and scandium oxide composite stabilized zirconia comprises the following steps:
heating a mixed aqueous solution of zirconium oxychloride, scandium oxide and holmium oxide, adjusting the pH value to obtain a mixed slurry, and then filtering, washing, drying, calcining and grinding;
in the mixed aqueous solution, the molar ratio of zirconium ions to scandium ions to holmium ions is (92-93): 6-7): 1.
The invention successfully inhibits the transformation of the cubic structure of the zirconia stabilized by scandium oxide to the rhombohedral structure by doping holmium oxide with a specific dosage, so that the obtained holmium oxide and scandium oxide composite stabilized zirconia has excellent ionic conductivity.
In one embodiment, the molar ratio of zirconium ions, scandium ions, and holmium ions in the mixed aqueous solution is 92:7: 1.
Preferably, the concentration of the zirconium oxychloride in the mixed aqueous solution is 0.02-0.6 mol/L.
In one embodiment, the concentration of zirconium oxychloride in the aqueous mixture solution is 0.02 to 0.6mol/L, and optionally 0.02mol/L, 0.05mol/L, 0.1mol/L, 0.15mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.35mol/L, 0.4mol/L, 0.45mol/L, 0.5mol/L, 0.55mol/L, or 0.6 mol/L.
Preferably, the heating temperature is 98-100 ℃, and the heating time is 96-120 h.
In one embodiment, the heating temperature is 98-100 ℃, and 98 ℃, 99 ℃ or 100 ℃ can be selected.
In one embodiment, the heating time is 96-120 h, and 96h, 100h, 105h, 110h, 115h or 120h can be selected.
Preferably, ammonia is used for adjusting the pH.
And adjusting the pH value of the heated solution to 7-8.
In one embodiment, the pH of the heated solution is adjusted to 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, or 8.
The invention adjusts the solution after reaction by adding ammonia water to form ZrO2·nH2And mixing the O, scandium hydroxide and holmium hydroxide to form slurry.
Preferably, the filtration is by pressure filtration and/or suction filtration.
And washing until no chloride ions exist.
And repeatedly washing for 5 times through filter pressing or suction filtration to remove chloride ions, and titrating and detecting with silver nitrate until no chloride ions exist. And further drying a filter cake obtained after filtering and washing.
The drying temperature is 115-125 ℃, and the drying time is 20-25 h.
In one embodiment, the drying temperature is 115-125 ℃, and 115 ℃, 116 ℃, 117 ℃, 118 ℃, 119 ℃, 120 ℃, 121 ℃, 122 ℃, 123 ℃, 124 ℃ or 125 ℃ can be selected.
In one embodiment, the drying time is 20-25 h, and can be 20h, 21h, 22h, 23h, 24h or 25 h.
Preferably, the calcining temperature is 600-900 ℃, and the calcining time is 1.5-2.5 h.
The powder is calcined in a muffle furnace or a push plate furnace for removing ZrO2·nH2And O, water molecules in scandium hydroxide and holmium hydroxide to obtain the anhydrous scandium oxide and holmium oxide composite stable zirconium oxide crystal.
In one embodiment, the temperature of the calcination is 600-900 ℃, and 600 ℃, 61 ℃, 650 ℃, 670 ℃, 690 ℃, 700 ℃, 720 ℃, 750 ℃, 780 ℃, 800 ℃, 820 ℃, 850 ℃, 870 ℃ or 900 ℃ can be selected.
In an embodiment, the calcination time is 1.5 to 2.5 hours, and 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours, 2 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, or 2.5 hours can be selected.
Preferably, the grinding comprises: and mixing the calcined material, a dispersing agent and water for grinding.
The dispersant is selected from ammonium citrate and/or triethanolamine.
The addition amount of the dispersing agent is 0.4-0.6% of the mass of the calcined material.
In one embodiment, the amount of the dispersant added is 0.4% to 0.6% by mass of the calcined material, and may be selected from 0.4%, 0.45%, 0.5%, 0.55%, or 0.6%.
The mass ratio of the calcined material to the water used in the grinding process is (5-30) to (70-95).
The grinding is ball milling.
The ball milling time is 20-25 h.
In one embodiment, the ball milling time is 20-25 h, and can be 20h, 21h, 22h, 23h, 24h or 25 h.
The holmium oxide and scandium oxide composite stabilized zirconia is prepared by the preparation method of the holmium oxide and scandium oxide composite stabilized zirconia.
An electrolyte material of a solid oxide fuel cell is mainly prepared from the holmium oxide and scandium oxide composite stabilized zirconia.
Preferably, the electrolyte material of the solid oxide fuel cell is mainly obtained by performing spray granulation on a mixture of the holmium oxide and scandium oxide composite stabilized zirconia and a binder;
the addition amount of the binder is 0.4-0.6% of the mass of the holmium oxide and scandium oxide composite stabilized zirconia.
In one embodiment, the addition amount of the binder is 0.4% to 0.6% of the mass of the holmium oxide and scandium oxide composite stabilized zirconia, and 0.4%, 0.45%, 0.5%, 0.55% or 0.6% can be selected.
The binder is selected from PVA.
The invention will be further explained with reference to specific examples.
Example 1
A preparation method of holmium oxide and scandium oxide composite stabilized zirconia powder comprises the following steps:
weighing 6.44Kg of zirconium oxychloride octahydrate, dissolving the zirconium oxychloride octahydrate in 1000L of water in an enamel reaction kettle, wherein the pH value of the completely dissolved solution is less than 1, then respectively weighing 1.932Kg of scandium oxide and 0.756Kg of holmium oxide, dissolving the scandium oxide and the holmium oxide in the acid solution, heating the solution to 60 ℃ to completely dissolve the scandium oxide and the holmium oxide, wherein the molar ratio of zirconium ions to the scandium ions to the holmium ions in the obtained solution is 92:7:1, and the concentration of the zirconium ions is 0.2 mol/L; heating the reactor to 100 ℃ to reach a boiling state, and performing hydrolysis reaction for 120 hours; after the reaction is finished, titrating the solution containing the white turbid matters by using ammonia water with the concentration of 1mol/L until the pH value of the solution is about 7, stopping titrating, washing the titrated solution by using a filter press, repeating for 5 times until no precipitate is formed in the dropwise added silver nitrate solution, and determining that chloride ions are completely washed away; drying a filter cake obtained by washing by a filter press at 120 ℃ for 24 hours, and calcining the dried powder in a muffle furnace by heating to 700 ℃ and preserving heat for 2 hours; and transferring the calcined powder into a horizontal ball mill, mixing the calcined powder with water to prepare a solution with the solid content of 30%, adding 45g of ammonium citrate as a dispersing agent, carrying out ball milling for 24 hours, stirring in a circulating sand mill, carrying out circulating ball milling for 10 times, and pumping the ball-milled slurry into a spray granulator by using a peristaltic pump for granulation to obtain the final product. The primary particle size is 40-50nm by transmission electron microscope observation. The appearance of the obtained holmium oxide and scandium oxide composite stabilized zirconia powder by a transmission electron microscope is shown in figure 1.
Example 2
A preparation method of holmium oxide and scandium oxide composite stabilized zirconia powder comprises the following steps:
weighing 12.88Kg of zirconium oxychloride octahydrate, dissolving the zirconium oxychloride octahydrate in 1000L of deionized water in an enamel reaction kettle, wherein the pH value of the completely dissolved solution is less than 1, then respectively weighing 3.733Kg of scandium oxide and 1.512Kg of holmium oxide, dissolving the scandium oxide and the holmium oxide in the acid solution, heating the solution to 60 ℃ to completely dissolve the scandium oxide and the holmium oxide, wherein the molar ratio of zirconium ions to scandium ions to holmium ions in the final solution is 92:7:1, and the concentration of the zirconium ions is 0.4 mol/L; heating the reactor to 100 ℃ to reach a boiling state, and performing hydrolysis reaction for 120 hours; after the reaction is finished, titrating the solution containing the white turbid substances by using ammonia water with the concentration of 1mol/L until the pH value of the solution is about 7, and stopping titration; washing the titrated solution by using a filter press, repeating for 5 times until no precipitate is formed in the dropwise added silver nitrate solution, and determining to completely wash away the chloride ions; then drying a filter cake obtained after washing by the filter press at the temperature of 120 ℃ for 24 hours; putting the dried powder into a muffle furnace, heating to 700 ℃, and keeping the temperature for 2 hours for calcination; and transferring the calcined powder into a horizontal ball mill, mixing the calcined powder with water to prepare a solution with the solid content of 30%, adding 90g of ammonium citrate serving as a dispersing agent, carrying out ball milling for 24 hours, transferring the mixture into a stirring and circulating sand mill, and carrying out circulating ball milling for 10 times. And pumping the ball-milled slurry into a spray granulator by using a peristaltic pump for granulation to obtain a final product. The primary particle size was around 10nm as observed by transmission electron microscopy. The transmission electron microscope topography of the obtained holmium oxide and scandium oxide composite stabilized zirconia powder is shown in fig. 2.
Example 3
A method of preparing an electrolyte material for a solid oxide fuel cell, comprising the steps of:
weighing 6.44Kg of zirconium oxychloride octahydrate, dissolving the octahydrate in 1000L of water in an enamel reaction kettle, wherein the pH value of a completely dissolved solution is less than 1, then respectively weighing 1.932Kg of scandium oxide and 0.756Kg of holmium oxide, dissolving the solutions in the acid solution, heating the solutions to 60 ℃ to completely dissolve the solutions, and finally obtaining a solution with the molar ratio of zirconium ions to scandium ions to holmium ions being 92:7:1 and the concentration of zirconium ions being 0.2 mol/L; heating the reactor to 100 ℃ to reach a boiling state, and performing hydrolysis reaction for 120 hours; after the reaction is finished, titrating the solution containing the white turbid substances by using ammonia water with the concentration of 1mol/L until the pH value of the solution is about 7, and stopping titration; washing the titrated solution by using a filter press, repeating for 5 times until no precipitate is formed in the dropwise added silver nitrate solution, and determining to completely wash away the chloride ions; then drying a filter cake obtained after washing by the filter press at the temperature of 120 ℃ for 24 hours; putting the dried powder into a muffle furnace, heating to 700 ℃, and keeping the temperature for 2 hours for calcination; transferring the calcined powder into a horizontal ball mill, mixing the calcined powder with water to prepare a solution with the solid content of 30%, adding 45g of beta-alanine serving as a dispersing agent, carrying out ball milling for 24 hours, stirring in a circulating sand mill, and carrying out circulating ball milling for 10 times; and pumping the ball-milled slurry into a spray granulator by using a peristaltic pump for granulation, and adding 45g of PVA as a binder into the spray granulator so as to enable the final product to be easier to dry press, so as to obtain the final product after granulation. Through observation by a transmission electron microscope, the original particle size of the original holmium oxide and scandium oxide composite stable zirconia powder is 40-50 nm. The sphericity of the granulated powder is high, the size of the granulated ball is about 40 microns through observation of a scanning electron microscope, and the shape of the obtained powder is shown in a scanning electron microscope figure 3.
Experimental example 1
(1) As can be seen from fig. 4 and 5, the doping of a specific amount of holmium oxide in the present invention successfully suppresses the transformation of the cubic structure of the scandia-stabilized zirconia into the rhombohedral structure. The oxygen ion has the highest diffusion coefficient in the cubic zirconia, and the corresponding ion conductivity is also the best. The occurrence of rhombus structures seriously damages the ion conductivity of the zirconia material.
(2) As can be seen from fig. 6 and 7, the ion conductivity of the scandia-stabilized zirconia is improved by doping a specific amount of holmium oxide in the present invention, and the holmium oxide and scandia composite stabilized zirconia powder (7Sc1HoSZ) in the present invention is significantly higher than the currently known best zirconia material doped with 8 mol%, and is also higher than 7Sc3HoSZ and 7Sc5 HoSZ.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of holmium oxide and scandium oxide composite stabilized zirconia is characterized by comprising the following steps:
heating a mixed aqueous solution of zirconium oxychloride, scandium oxide and holmium oxide, adjusting the pH value to obtain a mixed slurry, and then filtering, washing, drying, calcining and grinding;
in the mixed aqueous solution, the molar ratio of zirconium ions to scandium ions to holmium ions is (92-93): 6-7): 1.
2. The method for preparing the holmium oxide and scandium oxide composite stabilized zirconia according to claim 1, wherein the concentration of the zirconium oxychloride in the mixed aqueous solution is 0.02-0.6 mol/L.
3. The method for preparing the holmium oxide and scandium oxide composite stabilized zirconia according to claim 1, wherein the heating is carried out at a temperature of 98-100 ℃ for 96-120 h.
4. The method for preparing the holmium oxide and scandium oxide composite stabilized zirconia powder according to claim 1, wherein ammonia water is used for adjusting the pH;
and adjusting the pH value of the heated solution to 7-8.
5. The method for preparing the holmium oxide and scandium oxide composite stabilized zirconia according to claim 1, wherein the filtering is performed by pressure filtration and/or suction filtration;
washing until no chloride ion exists;
the drying temperature is 115-125 ℃, and the drying time is 20-25 h.
6. The method for preparing the holmium oxide and scandium oxide composite stabilized zirconia according to claim 1, wherein the calcining temperature is 600-900 ℃ and the calcining time is 1.5-2.5 h.
7. The method for preparing the holmium oxide and scandium oxide composite stabilized zirconia according to any one of claims 1 to 6, wherein the grinding comprises: mixing the calcined material, a dispersing agent and water for grinding;
the dispersant is selected from ammonium citrate and/or triethanolamine;
the addition amount of the dispersing agent is 0.4-0.6% of the mass of the calcined material;
the mass ratio of the calcined material to the water used in the grinding process is (5-30) to (70-95);
the grinding is ball milling;
the ball milling time is 20-25 h.
8. The holmium oxide and scandium oxide composite stabilized zirconia obtained by the method for preparing the holmium oxide and scandium oxide composite stabilized zirconia according to any one of claims 1 to 7.
9. An electrolyte material for a solid oxide fuel cell, characterized by being mainly prepared from the holmium oxide and scandium oxide composite stabilized zirconia of claim 8.
10. The electrolyte material for solid oxide fuel cells according to claim 9, which is obtained by spray granulation of a mixture of mainly the holmium oxide and scandium oxide composite stabilized zirconia and a binder;
the addition amount of the binder is 0.4-0.6% of the mass of the holmium oxide and scandium oxide composite stabilized zirconia;
the binder is selected from PVA.
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