CN100353588C - Preparation method of solid oxide fuel battery electrolyte diaphram - Google Patents
Preparation method of solid oxide fuel battery electrolyte diaphram Download PDFInfo
- Publication number
- CN100353588C CN100353588C CNB2005101213114A CN200510121311A CN100353588C CN 100353588 C CN100353588 C CN 100353588C CN B2005101213114 A CNB2005101213114 A CN B2005101213114A CN 200510121311 A CN200510121311 A CN 200510121311A CN 100353588 C CN100353588 C CN 100353588C
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- preparation
- solid oxide
- oxide fuel
- diaphram
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 28
- 239000000446 fuel Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000007787 solid Substances 0.000 title claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- 238000007493 shaping process Methods 0.000 claims abstract description 7
- 238000005520 cutting process Methods 0.000 claims abstract description 3
- 238000007788 roughening Methods 0.000 claims abstract description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 238000007766 curtain coating Methods 0.000 claims description 9
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 230000002706 hydrostatic effect Effects 0.000 claims description 4
- 238000003475 lamination Methods 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 238000004080 punching Methods 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims 4
- 229920005989 resin Polymers 0.000 claims 2
- 239000011347 resin Substances 0.000 claims 2
- 238000005266 casting Methods 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 abstract description 3
- 230000032683 aging Effects 0.000 abstract 1
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 239000002001 electrolyte material Substances 0.000 abstract 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract 1
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QDZOEBFLNHCSSF-PFFBOGFISA-N (2S)-2-[[(2R)-2-[[(2S)-1-[(2S)-6-amino-2-[[(2S)-1-[(2R)-2-amino-5-carbamimidamidopentanoyl]pyrrolidine-2-carbonyl]amino]hexanoyl]pyrrolidine-2-carbonyl]amino]-3-(1H-indol-3-yl)propanoyl]amino]-N-[(2R)-1-[[(2S)-1-[[(2R)-1-[[(2S)-1-[[(2S)-1-amino-4-methyl-1-oxopentan-2-yl]amino]-4-methyl-1-oxopentan-2-yl]amino]-3-(1H-indol-3-yl)-1-oxopropan-2-yl]amino]-1-oxo-3-phenylpropan-2-yl]amino]-3-(1H-indol-3-yl)-1-oxopropan-2-yl]pentanediamide Chemical compound C([C@@H](C(=O)N[C@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CC(C)C)C(N)=O)NC(=O)[C@@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](CCCCN)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](N)CCCNC(N)=N)C1=CC=CC=C1 QDZOEBFLNHCSSF-PFFBOGFISA-N 0.000 description 2
- 102100024304 Protachykinin-1 Human genes 0.000 description 2
- 101800003906 Substance P Proteins 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Fuel Cell (AREA)
Abstract
The present invention relates to a preparation method for electrolyte diaphragms of solid oxide fuel cells. The present invention comprises the following steps: zirconium oxide with stabilizing agents is used as electrolyte materials, and is placed in a ball mill to disperse after a shaping auxiliary agent is added, and a PVB solution is added to be continuously mixed and ground to obtain slurry; the slurry is processed by vacuum defoamation and ageing; raw film belts are made by flow casting, and are tailored into raw films by moulds; the raw films are stacked according to required thickness and put into a still hydraulic press to press and synthesize blank sheets, the surfaces are processed by roughening, and then, the blank sheets are shaped by die cutting; the shaped blank sheets are placed in a kiln for sintering. The preparation method for electrolyte diaphragms of solid oxide fuel cells of the present invention is not influenced by the change of environment temperature and humidity, and can not cause blank belts to crack because of the thickness increase of the flow casting. The electrolyte diaphragms produced by the present invention has the advantages of compact structure, high electric conductivity at high temperature and high mechanical strength.
Description
Technical field
The present invention relates to a kind of preparation method of electrolyte membrance of fuel cell, especially a kind of preparation method of electrolyte membrance of Solid Oxide Fuel Cell.
Background technology
The monocell of Solid Oxide Fuel Cell (SOFC) is that configuration anode and negative electrode made on two faces of solid oxide electrolyte barrier film, and its electrolyte membrance manufacture method has two kinds of rolling formation and flow casting moldings.There are problems such as density unevenness is even, bad mechanical strength in the fuel battery electrolyte diaphram that adopts the rolling formation method to produce, has had a strong impact on the serviceability of electrolyte membrance.The fuel battery electrolyte diaphram that adopts the flow casting molding method to produce, because the powder specific area of employed full stabilized zirconia is big, mass defects such as curtain coating cracking appear easily, and the weather to manufacturing environment is very responsive, in general humidity environment, when curtain coating thickness surpassed 0.2mm, this defective was more prone to produce.Thereby electrolyte membrance is restricted as supporting substrate.
Summary of the invention
The invention provides a kind of preparation method of electrolyte membrance of Solid Oxide Fuel Cell, can overcome above-mentioned existing defective preferably, made electrolyte membrance pdm substrate intensity height, and can not influence quality because of the variation of production environment weather.
The technical solution adopted in the present invention is, a kind of preparation method of solid oxide fuel battery electrolyte diaphram carries out according to the following steps:
(1) to be added with the zirconia (ZrO of stabilizer
2) be electrolyte, drop in the ball mill behind the adding shaping assistant and disperseed 13～24 hours, add PVB solution continuation mix grinding again and obtained slurry in 13～24 hours;
(2) with this slurry 9.5 * 10
4～10
5The subnormal ambient of Pa keeps carrying out in 10～30 minutes vacuum defoamation down, and continues 6～12 hours old processing;
(3) carry out curtain coating and make living film band, become to give birth to diaphragm through die for cutting again;
(4) will give birth to diaphragm by 2～3 layers of needed thickness laminations, and put into then under the condition of hydrostatic press with 50～90 ℃ of pressure 30～60MPa, temperature and be pressed into the base sheet, pressing time is 20～40 minutes;
(5) the base sheet is made surperficial roughening treatment, punching molding again;
(6) with the base of moulding klining knot on chip.
Described stabilizer is 3～10 mol% scandium oxide (Sc
2O
3) and 0.5～2mol% cerium oxide (CeO
2); Or 3～10mol% yittrium oxide (Y
2O
3); Or 0～8mol% scandium oxide and 3～6mol% yittrium oxide.
Described shaping assistant comprises dispersant and toluene, isopropyl alcohol mixed solvent.Dispersant and solvent adding amount account for 0.5～3.0% and 30～50% of electrolyte respectively, and PVB solution addition is 30～45%.
Preparation fuel battery electrolyte diaphram method of the present invention is not made the influence that ambient temperature and humidity change, and can not cause the cracking of base band because curtain coating thickness increases.The electrolyte membrance compact structure of being produced, high-temperature conductivity height, mechanical strength height.The present invention is suitable for plant layout production, can enhance productivity, and reduces cost, and environmental pollution is less.
Embodiment
Embodiment 1: weighing is zirconia (ZrO2) material of stabilizer with 3～10mol% scandium oxide (Sc2O3) and 0.5～1mol% cerium oxide (CeO2), it is put into shaping assistants such as the toluene for preparing in advance, isopropyl alcohol, dispersants disperse 13～24 hours in the ball mill.Then, add suitable substance P VB solution, continuation mix grinding pulp after 13～24 hours.Through vacuum defoamation and old processing, and it is qualified to measure viscosity, carries out curtain coating again this slurry.The living film band that curtain coating is come out is through the mould punching and shaping, through 3 layers of laminations, then in the hydrostatic press with the pressure of 35MPa under pressing 30 minutes, and surface coarsening handles, and becomes product after last sintering and the quality inspection.The specification of made fuel battery electrolyte diaphram is 99.5mm * 99.5mm, and thickness is 0.30mm, and the front surface roughness is 0.4～1.0 μ m, and back of the body surface roughness is 0.2～0.6 μ m, angularity≤0.05/25.4mm, bulk density 6.0g/cm
3
Embodiment 2: weighing is with 8mol% yittrium oxide (Y
2O
3) be the zirconia (ZrO of stabilizer
2) material, after handling, the process procedure identical with embodiment 1 become product.The specification of made fuel battery electrolyte diaphram is 300mm * 300mm, and thickness is 0.05～0.3mm, and front surface roughness Ra is 0.4～1.0 μ m, and back of the body surface roughness is 0.2～0.6 μ m, angularity≤0.06/25.4mm.Bulk density is 5.9g/cm
3
Embodiment 3: weighing 0～8moL% scandium oxide (Sc
2O
3) and 3～6mol% yittrium oxide (Y
2O
3) be the zirconia (ZrO of stabilizer
2) material, it is put into shaping assistants such as the toluene for preparing in advance, isopropyl alcohol, dispersants disperse 13～24 hours in the ball mill.Then, add suitable substance P VB solution, continuation mix grinding pulp after 13～24 hours.Through vacuum defoamation and old processing, and it is qualified to measure viscosity, carries out curtain coating again this slurry.The living film band that curtain coating is come out is die-cut into annular through mould, through 2 layers of laminations, then in the hydrostatic press with the pressure of 35MPa under pressing 30 minutes, and surface coarsening handles, and becomes product after last sintering and the quality inspection.The electrolyte membrance internal diameter is that 20mm, external diameter are that 120mm, thickness are 140 μ m, and the front surface roughness is 0.4～1.0 μ m, and back of the body surface roughness Ra is 0.2～0.6 μ m, angularity≤0.08/25.4mm.Bulk density is 6.0g/cm
3
Claims (3)
1, a kind of preparation method of solid oxide fuel battery electrolyte diaphram is characterized in that: realize according to the following steps:
(1) to be added with the zirconia (ZrO of stabilizer
2) be electrolyte, add to drop in the ball mill behind the shaping assistant contain dispersant and toluene, isopropyl alcohol mixed solvent and disperseed 13～24 hours, add polyvinyl butyral resin (PVB) solution again and continue mix grinding and obtained slurry in 13～24 hours;
(2) with this slurry 9.5 * 10
4～10
5The subnormal ambient of Pa keeps carrying out in 10～30 minutes vacuum defoamation down, and continues 6～12 hours old processing;
(3) carry out curtain coating and make living film band, become to give birth to diaphragm through die for cutting again;
(4) will give birth to diaphragm by 2～3 layers of needed thickness laminations, and put into the hydrostatic press then and be pressed into the base sheet under the condition of 50～90 ℃ of pressure 30～60MPa, temperature, pressing time is 20～40 minutes;
(5) the base sheet is made surperficial roughening treatment, punching molding again;
(6) with the base of moulding klining knot on chip.
2, the preparation method of solid oxide fuel battery electrolyte diaphram according to claim 1 is characterized in that: described stabilizer is 3～10mol% scandium oxide (Sc
2O
3) and 0.5～2mol% cerium oxide (CeO
2); Or 3～10mol% yittrium oxide (Y
2O
3); Or 0～8mol% scandium oxide and 3～6mol% yittrium oxide.
3, the preparation method of solid oxide fuel battery electrolyte diaphram according to claim 1, it is characterized in that: dispersant and solvent adding amount account for 0.5～3.0% and 30～50% of electrolyte respectively, and polyvinyl butyral resin (PVB) solution addition is 30～45%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101213114A CN100353588C (en) | 2005-12-26 | 2005-12-26 | Preparation method of solid oxide fuel battery electrolyte diaphram |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101213114A CN100353588C (en) | 2005-12-26 | 2005-12-26 | Preparation method of solid oxide fuel battery electrolyte diaphram |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1794486A CN1794486A (en) | 2006-06-28 |
| CN100353588C true CN100353588C (en) | 2007-12-05 |
Family
ID=36805827
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101213114A Active CN100353588C (en) | 2005-12-26 | 2005-12-26 | Preparation method of solid oxide fuel battery electrolyte diaphram |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100353588C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130316267A1 (en) * | 2011-01-31 | 2013-11-28 | Toto Ltd. | Solid electrolyte material and solid oxide fuel cell provided the same |
| CN102495160B (en) * | 2011-11-15 | 2014-07-16 | 长沙骏姆测控设备有限公司 | Preparation technology of novel gas chromatography detector |
| CN103618101A (en) * | 2013-12-19 | 2014-03-05 | 湖南稀土金属材料研究院 | Electrolyte material for solid oxide fuel battery and preparation method of material |
| CN103647097B (en) * | 2013-12-20 | 2016-08-17 | 湖南稀土金属材料研究院 | Sc2o3stablize ZrO2base electrolyte powder body, its preparation method and Sc2o3stablize ZrO2electrolyte ceramics sheet |
| CN111129560B (en) * | 2019-12-27 | 2021-11-09 | 国联汽车动力电池研究院有限责任公司 | Oxide solid electrolyte sheet and preparation method and application thereof |
| CN113773076A (en) * | 2021-09-26 | 2021-12-10 | 苏州正义新能源科技有限公司 | Fuel cell electrolyte membrane with low sintering temperature and preparation method thereof |
| CN114300720A (en) * | 2021-12-31 | 2022-04-08 | 徐州华清京昆能源有限公司 | A method for improving the isotropy of solid oxide fuel cells |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1271969A (en) * | 1999-04-22 | 2000-11-01 | 中国科学院大连化学物理研究所 | Anode load type solid electrolyte of yttrium oxide stabilized zirconium oxide and its preparing process |
| CN1277096A (en) * | 2000-06-16 | 2000-12-20 | 吉林大学 | Vacuum injection process of preparing electrolyte film tube and its forming equipment |
| JP2005276536A (en) * | 2004-03-23 | 2005-10-06 | Dainippon Printing Co Ltd | Solid oxide fuel cell |
-
2005
- 2005-12-26 CN CNB2005101213114A patent/CN100353588C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1271969A (en) * | 1999-04-22 | 2000-11-01 | 中国科学院大连化学物理研究所 | Anode load type solid electrolyte of yttrium oxide stabilized zirconium oxide and its preparing process |
| CN1277096A (en) * | 2000-06-16 | 2000-12-20 | 吉林大学 | Vacuum injection process of preparing electrolyte film tube and its forming equipment |
| JP2005276536A (en) * | 2004-03-23 | 2005-10-06 | Dainippon Printing Co Ltd | Solid oxide fuel cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1794486A (en) | 2006-06-28 |
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