CN100432013C - Sub-micron zirconium oxide electrolyte film material and its prepn process - Google Patents
Sub-micron zirconium oxide electrolyte film material and its prepn process Download PDFInfo
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- CN100432013C CN100432013C CNB2005100635570A CN200510063557A CN100432013C CN 100432013 C CN100432013 C CN 100432013C CN B2005100635570 A CNB2005100635570 A CN B2005100635570A CN 200510063557 A CN200510063557 A CN 200510063557A CN 100432013 C CN100432013 C CN 100432013C
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- 239000000463 material Substances 0.000 title claims abstract description 59
- 239000003792 electrolyte Substances 0.000 title claims abstract description 37
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims description 31
- 229910001928 zirconium oxide Inorganic materials 0.000 title claims description 31
- 238000000034 method Methods 0.000 title abstract description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000005245 sintering Methods 0.000 claims abstract description 19
- 238000005516 engineering process Methods 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- 229910052573 porcelain Inorganic materials 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 2
- 239000011164 primary particle Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- VWQVUPCCIRVNHF-BJUDXGSMSA-N yttrium-88 Chemical compound [88Y] VWQVUPCCIRVNHF-BJUDXGSMSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 239000010409 thin film Substances 0.000 abstract description 6
- 239000007784 solid electrolyte Substances 0.000 abstract description 4
- 230000035939 shock Effects 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 25
- 239000000919 ceramic Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 7
- 239000000446 fuel Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000000280 densification Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 229910002078 fully stabilized zirconia Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention discloses sub-micron zirconia electrolyte thin-film material and a preparing method thereof, which belongs to the technical field of electrolyte thin film material. In order to solve the problem that the prior art can not be utilized to prepare sub-micron zirconia electrolyte thin film material, the present invention provides a preparing method which has simple technology and is realized through sintering under low temperatures of 1200 to 1300 DEG C. The prepared thin film material has favorable electric conductivity and has the electric conductivity of 0.130 to 0.150 S/cm and the grain size of 0.1 to 1 mum under 1000 DEG C, which belongs to the sub-micron magnitude, so that the strength and the thermal shock resistant property are enhanced, and requirements for the combination property of devices for preparing zirconia solid electrolyte are satisfied.
Description
Technical field
The present invention relates to a kind of preparation method of electrolyte film material, more particularly, the present invention relates to a kind of preparation method of Zirconia electrolytic film material.
Background technology
Zirconia ceramics is used widely in refractory materials, high-temperature structural material and field of electronic materials with its excellent physics, chemical property.In fire resisting material field was used, the sintering temperature of zirconia ceramics was usually more than 1600-1700 ℃.As high-temperature structural material, adopt PSZ usually, sintering temperature is at 1400～1700 ℃.It is 0.1～0.3 μ m zirconia ceramics that patent 200410006012 has obtained grain-size at 1200～1400 ℃ of following sintering, but the performance of this pottery also mainly shows high strength and high tenacity, suitable to the use of structural ceramics device.
As field of functional materials, mainly is the zirconia ceramics of complete stable cubic structure at zirconium white, has good oxygen-ion conduction performance, is widely used in industries such as transmitter, concentration cell, fuel cells.When zirconium white is used in above-mentioned field, adopt film class material usually, to improve working performance of devices.Because material is made film like, its corresponding mechanical property just can not well meet the demands.Therefore wish to reduce the grain-size of zirconia ceramics, improve its mechanical property, and guarantee that its electric property does not descend.But the zirconia ceramics as solid electrolyte mainly is the zirconium white of complete stable cubic crystal formation, adopts common ceramic preparation, and the zirconium white of complete stable cubic crystal formation is easy to grow up when sintering, and technology can't be controlled at sub-micrometer scale with it at present.Inventor's patent 02129594 has realized sintering in the 1300-1450 ℃ of scope, has prepared suitable Zirconia electrolytic film material for solid oxide fuel cell, and grain-size is at 1-5 μ m.
At the zirconia film material of above-mentioned Application Areas, wish thickness between 10-200 μ m, if crystal grain is controlled at below the 1 μ m, just can form the electrolyte film material of even compact.Present existing technology of preparing can't satisfy this point.
Wishing has a kind of technology to prepare close grain fully stabilized zirconia electrolyte film material, under the prerequisite that satisfies the conductivity requirement, grain refining helps to improve intensity, increases heat-shock resistance, satisfies the needs of the over-all properties of zirconia solid electrolyte thin-film material fabricate devices.
Summary of the invention
The present invention can't prepare the problem of the zirconia film material that is used as electrolytical complete stable cubic crystal formation of sub-micrometer scale in order to solve prior art, and a kind of preparation method of sub-micron zirconium oxide electrolyte film material is provided.
Concrete technical scheme of the present invention is as follows.
The preparation method of a kind of sub-micron zirconium oxide electrolyte film material of the present invention comprises the steps:
(1) ZrO of employing nano particle size
2Powder is a raw material, uses conventional flow casting molding, rolling formation or gel to annotate technology and makes ionogen base sheet, and base substrate thickness is 10-200 μ m, and relative density is 50-60%;
(2) the ionogen base sheet that step (1) is obtained carries out presintering, and the presintering system is as follows:
Be warming up to 200 ℃ from room temperature, heat-up rate is 60-200 ℃/h; Be warming up to 300-500 ℃ from 200, heat-up rate is 50-100 ℃/h; 300-500 ℃ temperature spot constant temperature 1-10 hour; Be warming up to 800-1000 ℃ from this thermostat temperature point, heat-up rate is 100-250 ℃/h; 800-1000 ℃ temperature spot constant temperature 1-10 hour; Naturally cool to room temperature and obtain the ionogen porcelain body;
(3) the ionogen porcelain body that step (2) is obtained carries out sintering, and sintering schedule is as follows:
Be warming up to 1400 ℃ from room temperature, heat-up rate is 60-500 ℃/h; Cool to 1200-1300 ℃ from 1400 ℃, cooling rate is 100-300 ℃/h; 1200-1300 ℃ temperature spot constant temperature 2-30 hour; Naturally cool to room temperature, obtain described sub-micron zirconium oxide electrolyte film material.
Selected powder granule is even more in the step (1), and it is narrow more to distribute, and the particle sphericity is good more, does not have hard aggregation in the particle, and the sub-micron zirconium oxide electrolyte film material crystal grain of preparing is even more, and porcelain body is fine and close more.Therefore when selecting raw material, select the suitable powder of these characteristics as raw material as far as possible.Described nanometer ZrO
2The performance of powder is preferably: primary particle granularity 15～50nm, N
2Absorption specific surface 10～70m
2/ g; Offspring concentrates on more than 85% between 0.10～0.60 μ m micron, and presents the main peak value in 0.3～0.4 μ m place.
Described nanometer ZrO
2As long as it is just passable that powder can form the complete stable cubic crystalline structure, the more preferably zirconium white that Y is stable, stable stable stable stable zirconium white and the stable zirconium white of Sc of zirconium white, Sm of zirconium white, Nd of zirconium white, Yb of zirconium white, Ca that Mg is stable.Content for these elements in the zirconium white does not limit especially, as long as it is just passable to form the complete stable cubic crystalline structure, can adopt known content range.
Described sub-micron zirconium oxide electrolyte film material has following composition: 8～12mol% yttrium oxide and 88～92mol% zirconium white.
In step (1), described flow casting molding, rolling formation or gel are annotated technology, and there is no particular limitation, adopts technology well known to those skilled in the art just passable.
In step (2) and (3), there is no particular limitation for all heat-up rates and cooling rate, can be uniformly, also can change, as long as just passable in desired velocity range.
Sub-micron zirconium oxide electrolyte film material among the present invention, thickness are 10-200 μ m, and relative density is not less than 96%, and its specific conductivity is 0.130-0.150S/cm in the time of 1000 ℃, and the average grain size in the material is 0.1-1 μ m.
Average grain size in the described material is preferably 0.1-0.5 μ m, more preferably 0.1-0.3 μ m.
Described relative density preferably is not less than 98%, further preferably is not less than 99%.
The preparation method of a kind of sub-micron zirconium oxide electrolyte film material of the present invention, technology is simple, is easy to realize industrialization.Because sintering temperature reduces, and makes production cost descend significantly.Sintering temperature is low, has suppressed complete stable cubic crystal formation zirconium white growing up when sintering, and particle diameter has been controlled at sub-micrometer scale, has improved intensity, has increased heat-shock resistance, satisfies the needs of the over-all properties of zirconia solid electrolyte thin-film material fabricate devices.Prepared sub-micron zirconium oxide electrolyte film material has good conductivity, mechanical property and thermal shock resistance, satisfies zirconia ceramics as Solid Oxide Fuel Cell, the needs of device application such as oxygen sensor.
Description of drawings
Fig. 1 is the electron scanning micrograph (SEM) of the sub-micron zirconium oxide electrolyte film material of embodiment 1.
Fig. 2 is the electron scanning micrograph (SEM) of the sub-micron zirconium oxide electrolyte film material of embodiment 2.
Fig. 3 is the electron scanning micrograph (SEM) of the sub-micron zirconium oxide electrolyte film material of embodiment 3.
Embodiment
Further explain the present invention in the mode of embodiment below, but the present invention is not limited to these embodiment.
Embodiment 1
Adopt 8mol%Y
2O
3Stable ZrO
2(being called for short YSZ), powder was a raw material, and the properties of powder index sees Table 1.Adopt film rolling forming process to prepare ionogen base sheet, the processing condition of base sheet presintering are room temperature-200 ℃, and the heating-up time is 1 hour; 200-500 ℃, the heating-up time is 3 hours; 500 ℃ of following constant temperature 2 hours; 500-1000 ℃, the heating-up time is 3 hours; 1000 ℃ of following constant temperature 2 hours; Naturally cool to room temperature.Carry out the porcelain body sintering then, sintering condition is a room temperature-1400 ℃, and the heating-up time is 4 hours, and 1400 ℃ cool to 1250 ℃, and temperature fall time is 0.5 hour; 1250 ℃ of following constant temperature 20 hours; Naturally cool to room temperature, obtain the sub-micron zirconium oxide electrolyte film material of present embodiment.The microscopic appearance of this material such as Fig. 1, magnification is 20000 times, grain-size is 0.1-0.3 μ m, evenly, densification.This material is in the time of 1000 ℃, and specific conductivity is 0.141S/cm, and conductivity is good, satisfies the needs of zirconia ceramics as device application such as Solid Oxide Fuel Cell, oxygen sensors, and concrete data results sees Table 2.
Embodiment 2
Adopt 8mol%Y
2O
3Stable ZrO
2(being called for short YSZ), powder was a raw material, and the properties of powder index sees Table 1.Adopt casting molding processes to prepare ionogen base sheet, the processing condition of base sheet presintering are room temperature-200 ℃, and the heating-up time is 1 hour; 200-500 ℃, the heating-up time is 6 hours; 500 ℃ of constant temperature 4 hours; 500-1000 ℃, the heating-up time is 5 hours; 1000 ℃ of constant temperature 6 hours; Naturally cool to room temperature.Carry out the porcelain body sintering then, sintering condition is a room temperature-1400 ℃, and the heating-up time is 3.5 hours, and 1400 ℃ cool to 1300 ℃, and temperature fall time is 20 minutes; 1300 ℃ of constant temperature 10 hours; Naturally cool to room temperature, obtain the sub-micron zirconium oxide electrolyte film material of present embodiment.The microscopic appearance of this material such as Fig. 2, magnification is 15000 times, and grain-size is 0.2-0.4 μ m, and evenly, crystal boundary is fuzzy, the porcelain body densification.This material is in the time of 1000 ℃, and specific conductivity is 0.137S/cm, and conductivity is good, satisfies the needs of zirconia ceramics as device application such as Solid Oxide Fuel Cell, oxygen sensors, and concrete data results sees Table 2.
Embodiment 3
Adopt 8mol%Y
2O
3Stable ZrO
2(being called for short YSZ), powder was a raw material, and the properties of powder index sees Table 1.Adopt the gel injection formation technology to prepare ionogen base sheet, the processing condition of base sheet presintering are room temperature-300 ℃, and the heating-up time is 1 hour; 300-500 ℃, the heating-up time is 4 hours; 500 ℃ of constant temperature 6 hours; 500-1000 ℃, the heating-up time is 4 hours; 1000 ℃ of constant temperature 4 hours.Carry out the porcelain body sintering then, sintering condition is a room temperature-1400 ℃, and the heating-up time is 4 hours, and 1400 ℃ cool to 1300 ℃, and temperature fall time is 0.5 minute; 1300 ℃ of constant temperature 20 hours; Naturally cool to room temperature, obtain the sub-micron zirconium oxide electrolyte film material of present embodiment.The microscopic appearance of this material such as Fig. 3, magnification is 20000 times.Grain-size is 0.2-0.8 μ m, evenly, and the porcelain body densification.This material is in the time of 1000 ℃, and specific conductivity is 0.135S/cm, and conductivity is good, satisfies the needs of zirconia ceramics as device application such as Solid Oxide Fuel Cell, oxygen sensors, and concrete data results sees Table 2.
The performance index of table 1YSZ powder
The conductivity (S/cm) of the material that table 2 embodiment 1-3 obtains
| The mensuration temperature (℃) | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| 550 | 0.003 | 0.002 | 0.003 |
| 600 | 0.004 | 0.003 | 0.005 |
| 650 | 0.007 | 0.008 | 0.009 |
| 700 | 0.011 | 0.014 | 0.016 |
| 750 | 0.024 | 0.026 | 0.027 |
| 800 | 0.039 | 0.038 | 0.041 |
| 850 | 0.054 | 0.052 | 0.057 |
| 900 | 0.077 | 0.072 | 0.075 |
| 950 | 0.104 | 0.101 | 0.101 |
| 1000 | 0.141 | 0.137 | 0.135 |
Claims (9)
1. the preparation method of a sub-micron zirconium oxide electrolyte film material is characterized in that, it may further comprise the steps:
(1) ZrO of employing nano particle size
2Powder is a raw material, uses conventional flow casting molding, rolling formation or gel to annotate technology and makes ionogen base sheet, and base substrate thickness is 10-200 μ m, and relative density is 50-60%;
(2) the ionogen base sheet that step (1) is obtained carries out presintering, and the presintering system is as follows:
Be warming up to 200 ℃ from room temperature, heat-up rate is 60-200 ℃/h; Be warming up to 300-500 ℃ from 200 ℃, heat-up rate is 50-100 ℃/h; 300-500 ℃ temperature spot constant temperature 1-10 hour; Be warming up to 800-1000 ℃ from this thermostat temperature point, heat-up rate is 100-250 ℃/h; 800-1000 ℃ temperature spot constant temperature 1-10 hour; Naturally cool to room temperature and obtain the ionogen porcelain body;
(3) the ionogen porcelain body that step (2) is obtained carries out sintering, and sintering schedule is as follows:
Be warming up to 1400 ℃ from room temperature, heat-up rate is 60-500 ℃/h; Cool to 1200-1300 ℃ from 1400 ℃, cooling rate is 100-300 ℃/h; 1200-1300 ℃ temperature spot constant temperature 2-30 hour; Naturally cool to room temperature, obtain described sub-micron zirconium oxide electrolyte film material.
2. the preparation method of sub-micron zirconium oxide electrolyte film material according to claim 1 is characterized in that, described nanometer ZrO
2The performance of powder is: primary particle granularity 15～50nm, N
2Absorption specific surface 10～70m
2/ g; Offspring concentrates on more than 85% between 0.10～0.60 μ m micron, and presents the main peak value in 0.3～0.4 μ m place.
3. the preparation method of sub-micron zirconium oxide electrolyte film material according to claim 1 is characterized in that, described nanometer ZrO
2Zirconium white that zirconium white, the Sm that zirconium white, the Nd that zirconium white, the Yb that zirconium white, the Ca that powder is the stable zirconium white of Y, Mg is stable is stable is stable is stable is stable and/or the stable zirconium white of Sc.
4. the preparation method of sub-micron zirconium oxide electrolyte film material according to claim 1, it is characterized in that, the thickness of described sub-micron zirconium oxide electrolyte film material is 10-200 μ m, relative density is not less than 96%, its specific conductivity is 0.130-0.150S/cm in the time of 1000 ℃, and the average grain size in the described sub-micron zirconium oxide electrolyte film material material is 0.1-1 μ m.
5. the preparation method of sub-micron zirconium oxide electrolyte film material according to claim 4 is characterized in that, the average grain size in the described sub-micron zirconium oxide electrolyte film material is 0.1-0.5 μ m.
6. the preparation method of sub-micron zirconium oxide electrolyte film material according to claim 4 is characterized in that, the average grain size in the described sub-micron zirconium oxide electrolyte film material is 0.1-0.3 μ m.
7. the preparation method of sub-micron zirconium oxide electrolyte film material according to claim 4 is characterized in that, described relative density is not less than 98%.
8. the preparation method of sub-micron zirconium oxide electrolyte film material according to claim 7 is characterized in that, described relative density is not less than 99%.
9. the preparation method of sub-micron zirconium oxide electrolyte film material according to claim 4 is characterized in that, described sub-micron zirconium oxide electrolyte film material has following composition: 8～12mol% yttrium oxide and 88～92mol% zirconium white.
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| CN102503415B (en) * | 2011-09-23 | 2014-04-16 | 广东风华高新科技股份有限公司 | Preparation method of compound zirconium oxide |
| CN107140976B (en) * | 2017-05-12 | 2021-04-16 | 中国科学院上海硅酸盐研究所 | Formula of zirconia electrolyte powder for oxygen sensor for vehicle |
| CN111348912A (en) * | 2020-03-20 | 2020-06-30 | 四川轻化工大学 | Solid oxide fuel cell dense electrolyte and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1469501A (en) * | 2002-09-09 | 2004-01-21 | 彭苏萍 | Zirconia electrolytic film material for solid oxide fuel cell and its prepn |
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| CN1469501A (en) * | 2002-09-09 | 2004-01-21 | 彭苏萍 | Zirconia electrolytic film material for solid oxide fuel cell and its prepn |
Non-Patent Citations (3)
| Title |
|---|
| YSZ 纳米粉料流延成型电解质薄膜性能研究. 韩敏芳.功能材料，第34卷第5期. 2003 * |
| 纳米粉体制备NO:P 电解质工艺性能研究. 韩敏芳.功能材料与器件学报，第9卷第3期. 2003 * |
| 轧膜成型YSZ 电解质薄片性能. 韩敏芳.电池，第34卷第3期. 2004 * |
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