CN102683728A - Anode-supported solid oxide fuel cell and preparation method thereof - Google Patents

Anode-supported solid oxide fuel cell and preparation method thereof Download PDF

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CN102683728A
CN102683728A CN2012101477038A CN201210147703A CN102683728A CN 102683728 A CN102683728 A CN 102683728A CN 2012101477038 A CN2012101477038 A CN 2012101477038A CN 201210147703 A CN201210147703 A CN 201210147703A CN 102683728 A CN102683728 A CN 102683728A
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anode
dielectric substrate
side dielectric
fuel cell
solid oxide
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杨绍华
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    • 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

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Abstract

The invention relates to the technical field of materials of fuel cells, in particular to an anode-supported solid oxide fuel cell, which is composed of an anode supporting layer, an anode functional layer, a fuel side electrolyte layer, an air side electrolyte layer and a cathode layer in sequence, wherein NiO+YSZ is used as the material of the anode supporting layer, the NiO+YSZ is used as the material of the anode functional layer, and YSZ and CeO2 or rare-earth-doped CeO2 are used as the materials of dual electrolytes. The invention further provides a preparation method of the anode-supported solid oxide fuel cell. For the anode-supported solid oxide fuel cell prepared by adopting the preparation method of the anode-supported solid oxide fuel cell, the power density and the mechanical strength of a monocell are increased through material and structure design, and the anode-supported solid oxide fuel cell has the advantages of good electric conductivity, high reliability, low cost and suitability for batch production; and by means of a thin layer casting process, not only is the thickness of the electrolytes reduced effectively, but also the compactness of the electrolytes is guaranteed.

Description

A kind of positive electrode support solid oxide fuel cell and preparation method thereof
Technical field
The present invention relates to the fuel cell material technical field, relate to a kind of positive electrode support solid oxide fuel cell and preparation method thereof especially.
Background technology
SOFC is the high-efficient full solid-state electrochemical energy conversion equipment that chemical energy is converted into electric energy, and its loss mainly concentrates on the internal resistance loss of electrolyte.
Existing Chinese patent notification number is that CN100479245C discloses a kind of intermediate temperature solid oxide fuel cell positive electrode support solid electrolyte complex film and preparation method thereof; Zirconia (YSZ) or the zirconia (SSZ) of scandia stabilized or two-layer composition of cerium oxide (CGO) dielectric substrate of doping gadolinium oxide that this composite membrane is 6～10% stabilized with yttrium oxide by the zirconia cermet anode and the weight ratio of nickel oxide-stabilized with yttrium oxide; Process through curtain coating; Composite membrane area 100 * 100 (mm) is more than 2; Electrolyte thickness 10～30 μ m, anode thickness 0.5～1.5mm.Preferred anodes is made up of NiO+ (6～10) %mol YSZ, and electrolyte is made up of a kind of among 8YSZ, SSZ or the CGO.
Though this composite membrane is smooth and meet instructions for use, has following shortcoming: (1) 8YSZ does electrolyte, and ionic conductivity is too low, and the product power density is low.Cathode material be prone to electrolyte in ZrO 2(zirconia) reaction influences the power of battery; (2) the CGO material electric conductivity is high, but owing to be prone to influenced reliability by the anode fuel gas reduction; (3) the SSZ ionic conductivity is high, but cost is high, and Sc (scandium) is at nature and rare, and supply does not catch up with, and can't form volume production; (4) NiO+ (6～10) the %mol YSZ strength of materials is low, and doing supporter can influence reliability.
Summary of the invention
Shortcoming to prior art; The invention provides a kind of positive electrode support solid oxide fuel cell, effectively improve the power density of monocell, improve the mechanical strength and the reliability of product through material and structural design; Reduce production costs, be applicable to mass production.
The present invention also provides a kind of preparation method of positive electrode support solid oxide fuel cell, through the thin layer casting technique, has both effectively reduced electrolytical thickness, has guaranteed electrolytical compactness again.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is:
A kind of positive electrode support solid oxide fuel cell is characterized in that: be made up of anode support, anode functional layer, fuel-side dielectric substrate, air side dielectric substrate and cathode layer successively;
Said anode support consist of NiO+YSZ; Wherein, YSZ is the zirconia of 2～6mol% stabilized with yttrium oxide, said anode functional layer consist of NiO+YSZ; Wherein, YSZ is the zirconia of 5～12mol% stabilized with yttrium oxide, the zirconia that consists of 5～12mol% stabilized with yttrium oxide of said fuel-side dielectric substrate, said air side dielectric substrate consist of cerium oxide or rare earth doped cerium oxide.
Use NiO (nickel oxide)+2～6YSZ (2～6mol% yttrium stable zirconium oxide) as the anode-supported layer material, improved the intensity of supporter and monocell effectively;
Use NiO (nickel oxide)+5～12YSZ (5～12mol% yttrium stable zirconium oxide) as the anode function layer material, improved the performance of three phase boundary effectively, reduced the monocell polarization resistance;
Use 5～12YSZ (5～12mol% yttrium stable zirconium oxide) and CeO 2(cerium oxide) or rear-earth-doped CeO 2As the two-electrolyte material, and make 5～12YSZ (5～12mol% yttrium stable zirconium oxide) near anode-side (fuel-side), CeO 2(cerium oxide) or rear-earth-doped CeO 2Near cathode side (air side), prevent negative electrode and ZrO effectively 2The reaction of (zirconia) has also prevented fuel gas and CeO effectively 2(cerium oxide) or rear-earth-doped CeO 2Reaction.
Wherein, said cathode layer is one or more in lanthanum strontium manganese, lanthanum strontium ferro-cobalt, lanthanum strontium cobalt, lanthanum barium ferro-cobalt, lanthanum ferronickel and the barium-cobalt-iron-niobium.
Alternatively, said anode-supported layer thickness is 0.1～1.0mm, and the anode function layer thickness is 5～30 μ m, and fuel-side dielectric substrate thickness is 0.5～15 μ m, and air side dielectric substrate thickness is 0.5～15 μ m.
A kind of preparation method like above-mentioned positive electrode support solid oxide fuel cell is characterized in that, may further comprise the steps:
(1) prepare anode support ceramic size, anode functional layer ceramic size, fuel-side dielectric substrate ceramic size and air side dielectric substrate ceramic size respectively, curtain coating makes anode support ceramic membrane band, anode functional layer ceramic membrane band, fuel-side dielectric substrate ceramic membrane band and air side dielectric substrate ceramic membrane band;
(2) with anode support ceramic membrane band, anode functional layer ceramic membrane band, fuel-side dielectric substrate ceramic membrane band and the lamination pressing in order of air side dielectric substrate ceramic membrane band, sintering;
(3) cathode material is processed the printing slurry, be printed on the air side dielectric substrate, negative electrode advances the stove sintering.
Compared with prior art, the invention has the beneficial effects as follows:
Positive electrode support solid oxide fuel cell of the present invention uses 5～12YSZ (5～12mol% yttrium stable zirconium oxide) and CeO 2(cerium oxide) or rear-earth-doped CeO 2As the two-electrolyte material, and make 5～12YSZ (5～12mol% yttrium stable zirconium oxide) near anode-side (fuel-side), CeO 2(cerium oxide) or rear-earth-doped CeO 2Near cathode side (air side), prevent negative electrode and ZrO effectively 2The reaction of (zirconia) has also prevented fuel gas and CeO effectively 2(cerium oxide) or rear-earth-doped CeO 2Reaction, improved the reliability of positive electrode support solid oxide fuel cell greatly;
Introduce lower cost materials, use NiO (nickel oxide)+2～6YSZ (2～6mol% yttrium stable zirconium oxide) as anode-supported layer material, NiO (nickel oxide)+5～12YSZ (5～12mol% yttrium stable zirconium oxide) as anode function layer material, 5～12YSZ (5～12mol% yttrium stable zirconium oxide) and CeO 2(cerium oxide) or rear-earth-doped CeO 2As the two-electrolyte material, can be suitable for mass production.
The preparation method of positive electrode support solid oxide fuel cell of the present invention; But adopt the low-cost casting technique of mass production to make anode support, anode functional layer and dielectric substrate; Adopt typography to make cathode layer; Effectively reduce the thickness (0.5～15 μ m) of dielectric substrate through the thin layer casting technique, and use the CeO of macroion conduction 2(cerium oxide) or rear-earth-doped CeO 2As electrolyte, improved the conductive capability of electrolyte ion; Use NiO (nickel oxide)+5～12YSZ (5～12mol% yttrium stable zirconium oxide) as the anode function layer material; Co-sintering after anode support, anode functional layer and the two-electrolyte layer raw chip laminating pressing one has effectively improved the performance of anode and electrolyte interface.
Description of drawings
Fig. 1 is the profile of positive electrode support solid oxide fuel cell of the present invention.
Embodiment
Below in conjunction with embodiment the present invention is further described.
Be illustrated in figure 1 as the embodiment of positive electrode support solid oxide fuel cell of the present invention, this positive electrode support solid oxide fuel cell is made up of anode support 1, anode functional layer 2, fuel-side dielectric substrate 3, air side dielectric substrate 4 and cathode layer 5 successively.
Prepare anode support 1 ceramic size at first respectively, its composition is 5YSZ (5mol% yttrium stable zirconium oxide)+NiO (nickel oxide) of 1:1; Anode functional layer 2 ceramic sizes, its composition are 10YSZ (10mol% yttrium stable zirconium oxide)+NiO (nickel oxide) of 1:1; Fuel-side dielectric substrate 3 ceramic sizes, its composition are 10YSZ (10mol% yttrium stable zirconium oxide); Air side dielectric substrate 4 ceramic sizes, its composition are GOC (gallium doped cerium oxide);
Then make anode support 1 ceramic membrane band, anode functional layer 2 ceramic membrane bands, fuel-side dielectric substrate 3 ceramic membrane bands and air side dielectric substrate 4 ceramic membrane bands through casting method;
Then anode support 1 ceramic membrane band, anode functional layer 2 ceramic membrane bands, fuel-side dielectric substrate 3 ceramic membrane bands and air side dielectric substrate 4 ceramic membrane bands are carried out lamination pressing, sintering in order; On the air side dielectric substrate, print LSCF (lanthanum strontium ferro-cobalt) cathode layer 5 afterwards, carry out the negative electrode sintering at last.
Make positive electrode support solid oxide fuel cell by above-mentioned preparation method, its anode support 1 thickness is 0.5 mm, and anode functional layer 2 thickness are 15 μ m, and fuel-side dielectric substrate 3 thickness are 10 μ m, and air side dielectric substrate 4 thickness are 10 μ m.Record the power density of battery in the time of 800 ℃: 0.45W/cm2,1000hr decay: 0.31%.
The positive electrode support solid oxide fuel cell that adopts present embodiment positive electrode support solid oxide fuel cell preparation method to make; The power density of monocell and the mechanical strength of product have effectively been improved through material and structure Design; Conductive capability is good; Reliability is high, and cost is low, is suitable for mass production; Through the thin layer casting technique, both effectively reduced electrolytical thickness, guaranteed electrolytical compactness again.

Claims (5)

1. a positive electrode support solid oxide fuel cell is characterized in that: be made up of anode support, anode functional layer, fuel-side dielectric substrate, air side dielectric substrate and cathode layer successively.
2. positive electrode support solid oxide fuel cell according to claim 1 is characterized in that:
Said anode support consist of NiO+YSZ, wherein, YSZ is the zirconia of 2～6mol% stabilized with yttrium oxide,
Said anode functional layer consist of NiO+YSZ, wherein, YSZ is the zirconia of 5～12mol% stabilized with yttrium oxide,
The zirconia that consists of 5～12mol% stabilized with yttrium oxide of said fuel-side dielectric substrate,
Said air side dielectric substrate consist of cerium oxide or rare earth doped cerium oxide.
3. positive electrode support solid oxide fuel cell according to claim 2 is characterized in that: said cathode layer is one or more in lanthanum strontium manganese, lanthanum strontium ferro-cobalt, lanthanum strontium cobalt, lanthanum barium ferro-cobalt, lanthanum ferronickel and the barium-cobalt-iron-niobium.
4. positive electrode support solid oxide fuel cell according to claim 1; It is characterized in that: said anode-supported layer thickness is 0.1～1.0mm; The anode function layer thickness is 5～30 μ m, and fuel-side dielectric substrate thickness is 0.5～15 μ m, and air side dielectric substrate thickness is 0.5～15 μ m.
5. the preparation method like each described positive electrode support solid oxide fuel cell of claim 1 to 4 is characterized in that, may further comprise the steps:
Prepare anode support ceramic size, anode functional layer ceramic size, fuel-side dielectric substrate ceramic size and air side dielectric substrate ceramic size respectively, curtain coating makes anode support ceramic membrane band, anode functional layer ceramic membrane band, fuel-side dielectric substrate ceramic membrane band and air side dielectric substrate ceramic membrane band;
With anode support ceramic membrane band, anode functional layer ceramic membrane band, fuel-side dielectric substrate ceramic membrane band and the lamination pressing in order of air side dielectric substrate ceramic membrane band, sintering;
Cathode material is processed the printing slurry, be printed on the air side dielectric substrate, negative electrode advances the stove sintering.
CN2012101477038A 2012-05-14 2012-05-14 Anode-supported solid oxide fuel cell and preparation method thereof Pending CN102683728A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013173981A1 (en) * 2012-05-22 2013-11-28 Yang Shaohua Anode-supported solid oxide fuel cell and method for preparing same
CN103872367A (en) * 2012-12-13 2014-06-18 中国科学院大连化学物理研究所 Zirconia based electrolyte film of solid oxide fuel cell
CN103887549A (en) * 2012-12-21 2014-06-25 中国科学院大连化学物理研究所 Solid oxide fuel cell composite electrolyte film and preparation thereof
CN104037425A (en) * 2014-05-23 2014-09-10 景德镇陶瓷学院 Medium-temperature SOFC (solid oxide fuel cell) flat-plate anode-supported monocell anode structure and preparation method thereof
CN112952112A (en) * 2021-02-01 2021-06-11 浙江氢邦科技有限公司 Sintering method of solid oxide fuel cell

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CN1925200A (en) * 2006-08-18 2007-03-07 中国科学院上海硅酸盐研究所 Anode supporting solid electrolyte compound film for solid oxide fuel battery and its preparing method
CN101295792A (en) * 2007-04-24 2008-10-29 中国科学院大连化学物理研究所 Compound anode of solid-oxide fuel battery and method for producing the same
CN101399352A (en) * 2007-09-25 2009-04-01 中国科学院宁波材料技术与工程研究所 Producing method for a high strength ultra-thin anode supporting type solid oxide fuel cell
CN101599546A (en) * 2008-06-06 2009-12-09 中国科学院大连化学物理研究所 A kind of cathode material for solid-oxide fuel cell and application
CN202633438U (en) * 2012-05-14 2012-12-26 杨绍华 Anode support solid oxide fuel cell

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
CN1925200A (en) * 2006-08-18 2007-03-07 中国科学院上海硅酸盐研究所 Anode supporting solid electrolyte compound film for solid oxide fuel battery and its preparing method
CN101295792A (en) * 2007-04-24 2008-10-29 中国科学院大连化学物理研究所 Compound anode of solid-oxide fuel battery and method for producing the same
CN101399352A (en) * 2007-09-25 2009-04-01 中国科学院宁波材料技术与工程研究所 Producing method for a high strength ultra-thin anode supporting type solid oxide fuel cell
CN101599546A (en) * 2008-06-06 2009-12-09 中国科学院大连化学物理研究所 A kind of cathode material for solid-oxide fuel cell and application
CN202633438U (en) * 2012-05-14 2012-12-26 杨绍华 Anode support solid oxide fuel cell

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013173981A1 (en) * 2012-05-22 2013-11-28 Yang Shaohua Anode-supported solid oxide fuel cell and method for preparing same
CN103872367A (en) * 2012-12-13 2014-06-18 中国科学院大连化学物理研究所 Zirconia based electrolyte film of solid oxide fuel cell
CN103872367B (en) * 2012-12-13 2016-09-07 中国科学院大连化学物理研究所 A kind of SOFC zirconium oxide base electrolyte film
CN103887549A (en) * 2012-12-21 2014-06-25 中国科学院大连化学物理研究所 Solid oxide fuel cell composite electrolyte film and preparation thereof
CN103887549B (en) * 2012-12-21 2016-04-20 中国科学院大连化学物理研究所 A kind of Solid Oxide Fuel Cell composite electrolyte film and preparation thereof
CN104037425A (en) * 2014-05-23 2014-09-10 景德镇陶瓷学院 Medium-temperature SOFC (solid oxide fuel cell) flat-plate anode-supported monocell anode structure and preparation method thereof
CN112952112A (en) * 2021-02-01 2021-06-11 浙江氢邦科技有限公司 Sintering method of solid oxide fuel cell

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Application publication date: 20120919