CN107473737A - Combined oxidation zirconium powder for SOFC and preparation method thereof - Google Patents
Combined oxidation zirconium powder for SOFC and preparation method thereof Download PDFInfo
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- CN107473737A CN107473737A CN201710675422.2A CN201710675422A CN107473737A CN 107473737 A CN107473737 A CN 107473737A CN 201710675422 A CN201710675422 A CN 201710675422A CN 107473737 A CN107473737 A CN 107473737A
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- Prior art keywords
- sofc
- combined oxidation
- composite oxides
- zirconium powder
- preparation
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 230000003647 oxidation Effects 0.000 title claims abstract description 31
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 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
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 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 16
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 16
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 10
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide 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
- 239000000243 solution Substances 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000003595 mist Substances 0.000 claims description 6
- 239000004576 sand Substances 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000001514 detection method Methods 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 17
- 239000000446 fuel Substances 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 8
- 239000000843 powder Substances 0.000 abstract description 8
- 238000005452 bending Methods 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000007792 addition Methods 0.000 description 19
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 13
- 239000002002 slurry Substances 0.000 description 9
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NYWITVDHYCKDAU-UHFFFAOYSA-N oxygen(2-) yttrium(3+) zirconium(4+) Chemical compound [O--].[O--].[Y+3].[Zr+4] NYWITVDHYCKDAU-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 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
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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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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- C04B2235/02—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
- C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
- C04B2235/3203—Lithium oxide or oxide-forming salts thereof
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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Abstract
A kind of combined oxidation zirconium powder for SOFC of the invention and preparation method thereof, this method include adding composite oxides additive and PEG dispersants into zirconium oxychloride aqueous solution, and the composite oxides additive is by Al2O3、TiO2、CeO2、Bi2O3、Li2O is formed, the mass fraction scope that each composition of composite oxides additive accounts for total system is 0.2 5wt.%, through precipitating, being aged, filtering, the step such as washing, solid-oxide fuel battery electrolyte piece prepared by the combined oxidation zirconium powder being prepared, its electrical conductivity is 0.37s/cm, bending strength Kf at 800 DEG C>580MPa, it is not only able to meet the purposes as high-performance electrolyte in SOFC, and the preparation method of the present invention has the characteristics that to reunite less, particle diameter is small and even particle size distribution, powder active are high, easy-to-operate, suitable industrialized mass production.
Description
Technical field
It is more particularly to a kind of to be used for soild oxide the invention belongs to the field of production of SOFC
Combined oxidation zirconium powder of fuel cell and preparation method thereof.
Background technology
SOFC (Solid Oxide Full Cells, SOFC), is a kind of energy of high-efficiency cleaning
Converting system, the chemical energy of fuel gas and oxidizing gas can be directly changed into electric energy by it, and, response high with generating efficiency
Speed is fast, small volume, and pollution is low, the advantages that being easily assembled to and safeguard, is described as after hydroelectric generation, heat energy power-generating and nuclear energy power generation
A kind of efficient, energy-saving and environmental protection type generation technology afterwards.SOFC exploitation has turned into current new material with application and new energy is led
One study hotspot in domain.
Electrolyte is SOFC critical component, and at present, most SOFC are with 5~10mol% stabilized with yttrium oxide
Zirconium oxide as solid electrolyte, but its electrical conductivity is relatively low, and mechanical property is general, constrains SOFC further hair
Exhibition, therefore, finds the electrolyte new material that a kind of electrical conductivity is higher, mechanical property is stronger and ageing resistace is good, is to develop
The key of high-performance solid oxidate fuel cell.
Preparing electrolyte using the zirconium oxide of scandium oxide used as stabilizers has higher electrical conductivity, but mechanical property has
Declined, in terms of current result of study, individually using the oxidation of yittrium oxide or scandium oxide or a certain oxide used as stabilizers
Zirconium prepares electrolyte, and its combination property is not excellent, and the preparation technology using the zirconium oxide of many oxide doping also has
Some researchs, but do not have compared with quantum jump, the electrical conductivity for the zirconia electrolyte material that relatively good technology is prepared
About 0.12S/cm (at 800 DEG C), bending strength is about 500MPa.
Further investigation to crystal of zirconium oxide structure contributes to searching more suitably oxide to be doped, and has research table
It is bright, in zirconia system, due to the influence of dot matrix stress and steric effect, substitute Zr4+Cation radius it is closer with it,
Its electrical conductivity is higher.S.P.S.Badwal et al. is by 9mol% (Sc2O3-Y2O3)-ZrO2Al is added in system2O3It was found that
Al2O3Crystal boundary can be purified and reduce grain boundary resistance, increase the ZrO2The mechanical strength of based system, but add Al2O3Afterwards, ZrO2System
The electrical conductivity of system reduces very fast with the increase of cool time.Chakrapani Varanasi et al. have studied to be mixed into 6ScSZ
Miscellaneous Al2O3, as a result find Al2O3Addition improve 6ScSZ electrical conductivity, adulterate 30wt.%Al2O3When, 6ScSZ is at 850 DEG C
When electrical conductivity be 0.12S/cm, than being not added with Al2O3When electrical conductivity improve 20% or so.Masanori Hirano et al.
It has studied Bi2O3Adulterate 10ScSZ property, including sintering characteristic, microstructure, crystal transfer and electrical conductivity, mechanical property
Deng result of study shows：1mol%Bi is added into 10ScSZ2O3The crystal transfer of zirconium oxide can be effectively prevented, makes zirconium oxide
Cubic (high conductivity crystal formation) is effectively maintained, and therefore, adds 1mol%Bi2O3Afterwards, 10ScSZ electrical conductivity obtains
Improve.
Generally speaking, numerous studies have been done to the zirconium oxide of SOFC both at home and abroad at present, mainly
Including YSZ and ScSZ, and the stable type zirconium oxide of third phase is doped with, some preparation methods are only limitted to laboratory or small-sized system
It is standby, it is hardly formed industrialized production；The problems such as serious, sintering is difficult of reuniting be present in zirconia powder prepared by some methods；Some
The electrolyte that zirconia powder prepared by method is prepared can not meet the requirement that electrical conductivity is high, mechanical property is strong simultaneously.
The content of the invention
The technical problems to be solved by the invention are：A kind of reunion of offer is less, particle diameter is small and even particle size distribution, powder are lived
Property high, electrical conductivity is high, mechanical property the is strong combined oxidation zirconium powder for SOFC and preparation method thereof.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：One kind is used for solid oxide fuel electricity
The preparation method of the combined oxidation zirconium powder in pond, comprises the following steps：
Step 1, the zirconium oxychloride aqueous solution that zirconium oxychloride concentration is 0.5-1.5mol/L is prepared, be heated to 70 DEG C；Will
Sc2O3、Y2O3It is dissolved in and is heated in 70 DEG C of zirconium oxychloride aqueous solution, Sc after dissolving2O3Content be 1-7mol%, Y2O3's
Content is 1-7mol%；
Step 2, composite oxides additive and PEG dispersants, the composite oxides are added into step 1 resulting solution
Additive is by Al2O3、TiO2、CeO2、Bi2O3、Li2O is formed, and each composition of composite oxides additive accounts for the quality of total system
Fraction range is 0.2-5wt.%, and the mass fraction that the PEG dispersants account for total system is 0.2-0.5wt.%；
Step 3, urea is added into step 2 gains under agitation, the mass fraction that urea accounts for total system is 5-
10wt.%, is then slowly added into ammoniacal liquor, and regulation system pH value is 8.5-9.5；
Step 4, by step 3 gains be aged 2-6h, add reactor at 200-250 DEG C hydro-thermal reaction 6-18h；
Step 5, step 4 gains are filtered, are washed, circulation washing is first washed with deionized to excluding washings
Electrical conductivity is detected less than untill 150 μ s/cm, is finally washed 2 times with ethanol, filter cake is dried into 2-12h at 105 DEG C；
Step 6, dried block calcined into 1-6h at 650 DEG C -1000 DEG C；
Step 7, by the block after calcining after vibromill crushes, extra-fine grinding is carried out to median using sand mill
D50<0.2 μm, most afterwards through producing the combined oxidation zirconium powder for SOFC after mist projection granulating.
The present invention also provides a kind of preparation side using the above-mentioned combined oxidation zirconium powder for SOFC
The combined oxidation zirconium powder for SOFC that method is prepared.
The beneficial effects of the present invention are：Soild oxide combustion prepared by the combined oxidation zirconium powder that the above method is prepared
Expect cell electrolyte piece, its electrical conductivity is 0.37s/cm, bending strength Kf at 800 DEG C>580MPa, it is not only able to meet solid
Purposes in oxide fuel cell as high-performance electrolyte, and the present invention preparation method have energy consumption it is low, group
It is poly- less, the features such as particle diameter is small and even particle size distribution, powder active are high, easy-to-operate, be adapted to industrialized mass production.
Brief description of the drawings
Fig. 1 is the compound zirconia Powder Particle Size distribution map of the embodiment 2 of the specific embodiment of the invention.
Embodiment
To describe the technology contents of the present invention, the objects and the effects in detail, below in conjunction with embodiment and coordinate attached
Figure is explained.
The design of most critical of the present invention is：After composite oxides additive being added into zirconium oxychloride aqueous solution so that
The combined oxidation zirconium powder energy consumption for SOFC that is prepared is low, reunite less, particle diameter is small and size distribution
Uniformly, powder active is high, electrical conductivity is high, mechanical property is strong.
A kind of preparation method of combined oxidation zirconium powder for SOFC, comprises the following steps：
Step 1, the zirconium oxychloride aqueous solution that zirconium oxychloride concentration is 0.5-1.5mol/L is prepared, be heated to 70 DEG C；Will
Sc2O3、Y2O3It is dissolved in and is heated in 70 DEG C of zirconium oxychloride aqueous solution, Sc after dissolving2O3Content be 1-7mol%, Y2O3's
Content is 1-7mol%；
Step 2, composite oxides additive and PEG dispersants, the composite oxides are added into step 1 resulting solution
Additive is by Al2O3、TiO2、CeO2、Bi2O3、Li2O is formed, and each composition of composite oxides additive accounts for the quality of total system
Fraction range is 0.2-5wt.%, and the mass fraction that the PEG dispersants account for total system is 0.2-0.5wt.%；
Step 3, urea is added into step 2 gains under agitation, the mass fraction that urea accounts for total system is 5-
10wt.%, is then slowly added into ammoniacal liquor, and regulation system pH value is 8.5-9.5；
Step 4, by step 3 gains be aged 2-6h, add reactor at 200-250 DEG C hydro-thermal reaction 6-18h；
Step 5, step 4 gains are filtered, are washed, circulation washing is first washed with deionized to excluding washings
Electrical conductivity is detected less than untill 150 μ s/cm, is finally washed 2 times with ethanol, filter cake is dried into 2-12h at 105 DEG C；
Step 6, dried block calcined into 1-6h at 650 DEG C -1000 DEG C；
Step 7, by the block after calcining after vibromill crushes, extra-fine grinding is carried out to median using sand mill
D50<0.2 μm, most afterwards through producing the combined oxidation zirconium powder for SOFC after mist projection granulating.
The present invention also provides a kind of preparation side using the above-mentioned combined oxidation zirconium powder for SOFC
The combined oxidation zirconium powder for SOFC that method is prepared.
It was found from foregoing description, the beneficial effects of the present invention are：The combined oxidation zirconium powder system that the above method is prepared
Standby solid-oxide fuel battery electrolyte piece, its electrical conductivity are 0.37s/cm, bending strength Kf at 800 DEG C>580MPa,
It is not only able to meet the purposes as high-performance electrolyte in SOFC, and the preparation side of the present invention
Method has the characteristics that energy consumption is low, reunited less, particle diameter is small and even particle size distribution, powder active are high, easy-to-operate, is adapted to work
Industryization is produced in batches.
Embodiment 1
A kind of preparation method of combined oxidation zirconium powder for SOFC, it is concretely comprised the following steps：
(1) weigh zirconium oxychloride addition deionized water and be configured to the aqueous solution, concentration 1mol/L, be heated to 70 DEG C, will
Sc2O3、Y2O3It is dissolved in zirconyl chloride solution, the Sc2O3Content be 3mol%, the Y2O3Content be 7mol%, add
Enter composite oxides additive, composite oxides additive is by Al2O3、TiO2、CeO2、Bi2O3、Li2O is formed, and accounts for total system
Mass fraction is 4wt.%, wherein Al2O3Addition is 1.5wt.%, TiO2Addition is 0.5wt.%, CeO2Addition is
0.5wt.%, Bi2O3Addition is 1wt.%, Li2O additions are 0.5wt.%, add 0.2wt.% PEG dispersants；
(2) urea is added slowly with stirring, the mass fraction that urea accounts for total system is 5wt.%, is slowly added to ammoniacal liquor,
Hydrolytic precipitation, regulation slurry system pH value are 8.5；
(3) slurry of gained is aged 2h, adds in reactor the hydro-thermal reaction 18h at 230 DEG C；
(4) slurry after hydro-thermal is filtered, washed, circulation washing is first washed with deionized and is examined to washings are excluded
Electrical conductivity is surveyed less than untill 150 μ s/cm, is finally washed 2 times with ethanol, filter cake is dried into 6h at 105 DEG C.
(5) dried block is calcined into 3h at 650 DEG C.
(6) by the block after calcining after vibromill crushes, extra-fine grinding is carried out to median D50 using sand mill
For 0.15 μm, specific surface area 16m2/ g, most afterwards through just obtaining being suitable for SOFC after mist projection granulating
The combined oxidation zirconium powder of electrolyte, sintering temperature are 1280 DEG C, sintered density 5.9g/cm3.It is a kind of to be made with the present invention
Solid-oxide fuel battery electrolyte piece prepared by standby combined oxidation zirconium powder, its electrical conductivity is 0.31s/cm at 800 DEG C,
Bending strength Kf>530MPa.
Embodiment 2
A kind of preparation method of combined oxidation zirconium powder for SOFC, it is concretely comprised the following steps：
(1) weigh zirconium oxychloride addition deionized water and be configured to the aqueous solution, concentration 1mol/L, be heated to 70 DEG C, will
Sc2O3、Y2O3It is dissolved in zirconyl chloride solution, the Sc2O3Content be 5mol%, the Y2O3Content be 5mol%, add
Enter composite oxides additive, composite oxides additive is by Al2O3、TiO2、CeO2、Bi2O3、Li2O is formed, and accounts for total system
Mass fraction is 5wt.%, wherein Al2O3Addition is 2wt.%, TiO2Addition is 1wt.%, CeO2Addition is
0.5wt.%, Bi2O3Addition is 0.5wt.%, Li2O additions are 1wt.%, add 0.3wt.% PEG dispersants；
(2) urea is added slowly with stirring, the mass fraction that urea accounts for total system is 7wt.%, is slowly added to ammoniacal liquor,
Hydrolytic precipitation, regulation slurry system pH value are 9；
(3) slurry of gained is aged 3h, adds in reactor the hydro-thermal reaction 12h at 240 DEG C；
(4) slurry after hydro-thermal is filtered, washed, circulation washing is first washed with deionized and is examined to washings are excluded
Electrical conductivity is surveyed less than untill 150 μ s/cm, is finally washed 2 times with ethanol, filter cake is dried into 7h at 105 DEG C.
(5) dried block is calcined into 3h at 700 DEG C.
(6) by the block after calcining after vibromill crushes, extra-fine grinding is carried out to median D50 using sand mill
For 0.098 μm, size distribution is as shown in figure 1, specific surface area is 18m2/ g, most afterwards through just obtaining being suitable for admittedly after mist projection granulating
The combined oxidation zirconium powder of the electrolyte of oxide body fuel cell, sintering temperature are 1260 DEG C, sintered density 6.0g/
cm3.Solid-oxide fuel battery electrolyte piece prepared by a kind of combined oxidation zirconium powder prepared with the present invention, its electrical conductivity exist
It is 0.37s/cm, bending strength Kf at 800 DEG C>580MPa.
Embodiment 3
A kind of preparation method of combined oxidation zirconium powder for SOFC, it is concretely comprised the following steps：
(1) weigh zirconium oxychloride addition deionized water and be configured to the aqueous solution, concentration 1mol/L, be heated to 70 DEG C, will
Sc2O3、Y2O3It is dissolved in zirconyl chloride solution, the Sc2O3Content be 7mol%, the Y2O3Content be 3mol%, add
Enter composite oxides additive, composite oxides additive is by Al2O3、TiO2、CeO2、Bi2O3、Li2O is formed, and accounts for total system
Mass fraction is 1wt.%, wherein Al2O3Addition is 0.2wt.%, TiO2Addition is 0.2wt.%, CeO2Addition is
0.2wt.%, Bi2O3Addition is 0.2wt.%, Li2O additions are 0.2wt.%, add 0.3wt.% PEG dispersants；
(2) urea is added slowly with stirring, the mass fraction that urea accounts for total system is 5wt.%, is slowly added to ammoniacal liquor,
Hydrolytic precipitation, regulation slurry system pH value are 9.5；
(3) slurry of gained is aged 2h, adds in reactor the hydro-thermal reaction 6h at 240 DEG C；
(4) slurry after hydro-thermal is filtered, washed, circulation washing is first washed with deionized and is examined to washings are excluded
Electrical conductivity is surveyed less than untill 150 μ s/cm, is finally washed 2 times with ethanol, filter cake is dried into 8h at 105 DEG C.
(5) dried block is calcined into 2h at 800 DEG C.
(6) by the block after calcining after vibromill crushes, extra-fine grinding is carried out to median D50 using sand mill
For 0.18 μm, specific surface area 14m2/ g, most afterwards through just obtaining being suitable for SOFC after mist projection granulating
The combined oxidation zirconium powder of electrolyte, sintering temperature are 1300 DEG C, sintered density 5.8g/cm3.It is a kind of to be made with the present invention
Solid-oxide fuel battery electrolyte piece prepared by standby combined oxidation zirconium powder, its electrical conductivity is 0.35s/cm at 800 DEG C,
Bending strength Kf>515MPa.
Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to utilize this hair
The equivalents that bright specification and accompanying drawing content are made, or the technical field of correlation is directly or indirectly used in, similarly include
In the scope of patent protection of the present invention.
Claims (2)
- A kind of 1. preparation method of combined oxidation zirconium powder for SOFC, it is characterised in that：Including as follows Step：Step 1, the zirconium oxychloride aqueous solution that zirconium oxychloride concentration is 0.5-1.5mol/L is prepared, be heated to 70 DEG C；By Sc2O3、 Y2O3It is dissolved in and is heated in 70 DEG C of zirconium oxychloride aqueous solution, Sc after dissolving2O3Content be 1-7mol%, Y2O3Content be 1-7mol%；Step 2, composite oxides additive and PEG dispersants, the composite oxides addition are added into step 1 resulting solution Agent is by Al2O3、TiO2、CeO2、Bi2O3、Li2O is formed, and each composition of composite oxides additive accounts for the mass fraction of total system Scope is 0.2-5wt.%, and the mass fraction that the PEG dispersants account for total system is 0.2-0.5wt.%；Step 3, urea being added into step 2 gains under agitation, the mass fraction that urea accounts for total system is 5-10wt.%, Ammoniacal liquor is then slowly added into, regulation system pH value is 8.5-9.5；Step 4, by step 3 gains be aged 2-6h, add reactor at 200-250 DEG C hydro-thermal reaction 6-18h；Step 5, step 4 gains are filtered, are washed, circulation washing is first washed with deionized to excluding washings detection Untill electrical conductivity is less than 150 μ s/cm, finally washed 2 times with ethanol, filter cake is dried into 2-12h at 105 DEG C；Step 6, dried block calcined into 1-6h at 650 DEG C -1000 DEG C；Step 7, by the block after calcining after vibromill crushes, extra-fine grinding is carried out to median D50 using sand mill< 0.2 μm, most afterwards through producing the combined oxidation zirconium powder for SOFC after mist projection granulating.
- A kind of 2. preparation method system of the combined oxidation zirconium powder according to claim 1 for SOFC The standby obtained combined oxidation zirconium powder for SOFC.
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| CN111205088A (en) * | 2020-01-15 | 2020-05-29 | 中国恩菲工程技术有限公司 | Method for preparing scandia-stabilized zirconia powder by hydrothermal method and scandia-stabilized zirconia powder prepared by method |
| CN113004035A (en) * | 2019-12-20 | 2021-06-22 | 有研稀土新材料股份有限公司 | Rare earth modified zirconium-based oxide with nano core-shell structure |
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