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CN1794486A - Preparation method of solid oxide fuel battery electrolyte diaphram - Google Patents

Preparation method of solid oxide fuel battery electrolyte diaphram Download PDF

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Publication number
CN1794486A
CN1794486A CNA2005101213114A CN200510121311A CN1794486A CN 1794486 A CN1794486 A CN 1794486A CN A2005101213114 A CNA2005101213114 A CN A2005101213114A CN 200510121311 A CN200510121311 A CN 200510121311A CN 1794486 A CN1794486 A CN 1794486A
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China
Prior art keywords
preparation
diaphram
fuel battery
electrolyte
solid oxide
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CNA2005101213114A
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CN100353588C (en
Inventor
谢灿生
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Chaozhou Three Circle Group Co Ltd
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Chaozhou Three Circle Group Co Ltd
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Priority to CNB2005101213114A priority Critical patent/CN100353588C/en
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

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  • Fuel Cell (AREA)

Abstract

This invention relates to a preparation method for the electrolyte diaphragm of a solid oxide fuel battery including the following steps: 1, taking ZrO with a stabilizer as an electrolyte material, adding a molding agent in it to be scattered in a ball mill then adding PVB solution in it to be mixed and ground to get a slurry, 2, carrying out vacuum deaeration and ageing process, 3, processing in doctor-blade to manufacture a crude film strip to be cut by a die to generate crude film sheets, 4, laminating the crude film sheets according to the needs then to be put in a static water press to be pressed to a blank sheet to be processed roughly on the surface to be cut to a format, 5, putting the blank sheet in a stove to be sintered.

Description

A kind of preparation method of solid oxide fuel battery electrolyte diaphram
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 3~10mol% 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.
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, 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.
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 is characterized in that: 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%.
CNB2005101213114A 2005-12-26 2005-12-26 Preparation method of solid oxide fuel battery electrolyte diaphram Active CN100353588C (en)

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CNB2005101213114A CN100353588C (en) 2005-12-26 2005-12-26 Preparation method of solid oxide fuel battery electrolyte diaphram

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Application Number Priority Date Filing Date Title
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CN1794486A true CN1794486A (en) 2006-06-28
CN100353588C CN100353588C (en) 2007-12-05

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102495160A (en) * 2011-11-15 2012-06-13 长沙骏姆测控设备有限公司 Preparation technology of novel gas chromatography detector
CN103477483A (en) * 2011-01-31 2013-12-25 Toto株式会社 Solid electrolyte material and solid oxide fuel cell provided with same
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
CN103647097A (en) * 2013-12-20 2014-03-19 湖南稀土金属材料研究院 Sc2O3-stabilized ZrO2-based electrolyte powder and preparation method thereof, and Sc2O3-stabilized ZrO2 electrolyte ceramic wafer prepared from powder
CN111129560A (en) * 2019-12-27 2020-05-08 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

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1157815C (en) * 1999-04-22 2004-07-14 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
CN1114522C (en) * 2000-06-16 2003-07-16 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

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103477483A (en) * 2011-01-31 2013-12-25 Toto株式会社 Solid electrolyte material and solid oxide fuel cell provided with same
CN102495160A (en) * 2011-11-15 2012-06-13 长沙骏姆测控设备有限公司 Preparation technology of novel gas chromatography detector
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
CN103647097A (en) * 2013-12-20 2014-03-19 湖南稀土金属材料研究院 Sc2O3-stabilized ZrO2-based electrolyte powder and preparation method thereof, and Sc2O3-stabilized ZrO2 electrolyte ceramic wafer prepared from powder
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
CN111129560A (en) * 2019-12-27 2020-05-08 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

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