CN1847195A - 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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- CN1847195A CN1847195A CN 200510063557 CN200510063557A CN1847195A CN 1847195 A CN1847195 A CN 1847195A CN 200510063557 CN200510063557 CN 200510063557 CN 200510063557 A CN200510063557 A CN 200510063557A CN 1847195 A CN1847195 A CN 1847195A
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- 239000000463 material Substances 0.000 title claims abstract description 58
- 239000003792 electrolyte Substances 0.000 title claims abstract description 33
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001928 zirconium oxide Inorganic materials 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title abstract description 5
- 238000005516 engineering process Methods 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 74
- 238000005245 sintering Methods 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 17
- 229910052573 porcelain Inorganic materials 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 239000000758 substrate Substances 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
- 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
- VWQVUPCCIRVNHF-BJUDXGSMSA-N yttrium-88 Chemical compound [88Y] VWQVUPCCIRVNHF-BJUDXGSMSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 6
- 230000035939 shock Effects 0.000 abstract description 2
- 238000009766 low-temperature sintering Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 24
- 239000000919 ceramic Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 7
- 239000000446 fuel Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 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
- 239000007784 solid electrolyte Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000009826 distribution Methods 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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Abstract
The present invention discloses sub-micron zirconium oxide electrolyte film material and its preparation process, and belongs to the field of electrolyte film material preparing technology. The present invention provides one simple low temperature sintering process at 1200-1300 deg.c to prepare film material with high electric conductivity of 0.130-0.150 S/cm a 1000 deg.c, sub-micron level size of 0.1-1 micron, high strength and high heat shock resistance and possessing comprehensive performance for preparing solid zirconium oxide electrolyte film device.
Description
Technical field
The present invention relates to a kind of electrolyte film material and preparation method thereof, more particularly, the present invention relates to a kind of Zirconia electrolytic film material and preparation method thereof.
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 sub-micron zirconium oxide electrolyte film material and preparation method thereof is provided.
Concrete technical scheme of the present invention is as follows.
Sub-micron zirconium oxide electrolyte film material of 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%.
Sub-micron zirconium oxide electrolyte film material of the present invention is made by the preparation method who comprises the steps:
(1) adopting the ZrO2 powder of nano particle size is 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.The performance of described nanometer ZrO2 powder is preferably: primary particle granularity 15～50nm, N2 absorption specific surface 10～70m2/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.
As long as it is just passable that described nanometer ZrO2 powder can form the complete stable cubic crystalline structure, the more preferably zirconium white that Y is stable, the stable stable stable stable stable zirconium white of zirconium white, 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 of the present invention 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.Preparation method's technology provided by the invention 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.
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
Adopting the stable ZrO2 of 8mol%Y2O3 (being called for short YSZ) powder is 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
Adopting the stable ZrO2 of 8mol%Y2O3 (being called for short YSZ) powder is 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
Adopting the stable ZrO2 of 8mol%Y2O3 (being called for short YSZ) powder is 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
| Embodiment | The powder particle size (nm) that different methods is measured | Agglomerated particles particle diameter (μ m) | Specific surface (m 2·g -1) | The size-grade distribution width | The reunion coefficient | |||
| XRD | TEM | BET | Meso-position radius D 50 | Peak value footpath Dmod | ||||
| 1 | 9.04 | 10～15 | 15.84 | 0.99 | 0.71 | 62.50 | 14.58 | 62.50 |
| 2 | 16.95 | 30 | 40.84 | 1.05 | 2.58 | 25.71 | 18.94 | 25.71 |
| 3 | 22.60 | 50 | 71.12 | 0.49 | 0.16 | 6.89 | 8.91 | 6.89 |
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 (10)
1. a sub-micron zirconium oxide electrolyte film material is characterized in that, the thickness of described material is 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.
2. sub-micron zirconium oxide electrolyte film material according to claim 1 is characterized in that, the average grain size in the described material is 0.1-0.5 μ m.
3. sub-micron zirconium oxide electrolyte film material according to claim 1 is characterized in that, the average grain size in the described material is 0.1-0.3 μ m.
4. sub-micron zirconium oxide electrolyte film material according to claim 1 is characterized in that described relative density is not less than 98%.
5. sub-micron zirconium oxide electrolyte film material according to claim 1 is characterized in that described relative density is not less than 99%.
6. according to any described sub-micron zirconium oxide electrolyte film material among the claim 1-5, it is characterized in that it is made by following preparation method:
(1) adopting the ZrO2 powder of nano particle size is 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.
7. sub-micron zirconium oxide electrolyte film material according to claim 6 is characterized in that, the performance of described nanometer ZrO2 powder is: primary particle granularity 15～50nm, N2 absorption specific surface 10～70m2/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.
8. sub-micron zirconium oxide electrolyte film material according to claim 6, it is characterized in that the stable zirconium white of zirconium white, Sc that zirconium white, the Sm that zirconium white, the Nd that zirconium white, the Yb that zirconium white, the Ca that described nanometer ZrO2 powder is the stable zirconium white of Y, Mg is stable is stable is stable is stable is stable.
9. sub-micron zirconium oxide electrolyte film material according to claim 1 is characterized in that, described material has following composition: 8～12mol% yttrium oxide and 88～92mol% zirconium white.
10. the preparation method of any described sub-micron zirconium oxide electrolyte film material among the claim 1-9 is characterized in that it may further comprise the steps:
(1) adopting the ZrO2 powder of nano particle size is 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.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503415A (en) * | 2011-09-23 | 2012-06-20 | 广东风华高新科技股份有限公司 | Preparation method of compound zirconium oxide |
| CN107140976A (en) * | 2017-05-12 | 2017-09-08 | 中国科学院上海硅酸盐研究所 | A kind of oxygen sensor used in vehicle Zirconia electrolytic powder composition |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1204642C (en) * | 2002-09-09 | 2005-06-01 | 彭苏萍 | Zirconia electrolytic film material for solid oxide fuel cell and its prepn |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503415A (en) * | 2011-09-23 | 2012-06-20 | 广东风华高新科技股份有限公司 | Preparation method of compound zirconium oxide |
| 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 |
| CN107140976A (en) * | 2017-05-12 | 2017-09-08 | 中国科学院上海硅酸盐研究所 | A kind of oxygen sensor used in vehicle Zirconia electrolytic powder composition |
| 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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