CN101207218A - Method for preparation of tubular solid-oxide fuel battery - Google Patents
Method for preparation of tubular solid-oxide fuel battery Download PDFInfo
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- CN101207218A CN101207218A CNA2006101349462A CN200610134946A CN101207218A CN 101207218 A CN101207218 A CN 101207218A CN A2006101349462 A CNA2006101349462 A CN A2006101349462A CN 200610134946 A CN200610134946 A CN 200610134946A CN 101207218 A CN101207218 A CN 101207218A
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- oxide fuel
- fuel cell
- fuel battery
- tubular solid
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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
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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
- 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 a preparation method of a tubular solid oxide fuel cell (SOFC), and the tubular SOFC structure prepared through the method is a positive electrode supporting type solid oxide fuel cell. A positive electrode supporting pipe is molded through the plastic extrusion method; a dense electrolyte layer of a fuel cell is prepared outside the positive electrode supporting pipe by adopting the vacuum-dipcoating method, and a multiple hole negative electrode of the fuel cell is prepared through the brush painting method on the surface of the dense electrolyte layer. In order to improve the compactness of the electrolyte layer, the surface modification treatment is firstly required on the positive electrode supporting pipe. The tubular solid oxide fuel cell prepared by adopting the method of the invention can simplify the manufacturing process of the solid oxide fuel cell, greatly reduces the manufacturing cost of the solid oxide fuel cell, and pushes the development of the solid oxide fuel cell.
Description
Technical field:
The invention belongs to the energy, materials processing, relate to a kind of preparation of solid oxide fuel cell, particularly a kind of preparation method of tubular solid-oxide fuel battery.By simplifying the manufacturing process of tubular solid-oxide fuel battery, reduce manufacturing cost, promote the development of Solid Oxide Fuel Cell.
Background technology:
Fuel cell is called the 4th class new-generation technology after waterpower, firepower, nuclear energy technology by people, it is a kind of efficient green Blast Furnace Top Gas Recovery Turbine Unit (TRT) that directly chemical energy is converted into electric energy without external firing, be not subjected to the restriction of Carnot cycle, the utilance of fuel is very high.It is about 50% that the generating efficiency of its monocell can reach, and with the steam turbine combined cycle generation, generating efficiency can reach 70%, if reasonable use waste heat again, its heat efficiency can reach more than 80%.
Current, the structure type that Solid Oxide Fuel Cell usually adopts has cast and plate two kinds.By U.S.'s Westinghouse Electrical Corp. (Westinghouse Electric Crop.) development, it is formed by connecting in the series and parallel mode by the tubulose monocell of an end sealing cast SOFC battery the earliest.Each monocell is from inside to outside by the stable ZrO of porous C aO
2(being called for short CSZ) stay pipe, LSM air electrode, YSZ solid electrolyte film and Ni-YSZ cermet anode are formed.The CSZ antipriming pipe plays a supportive role and allows air freely to pass through to arrive air electrode.LSM air electrode, YSZ dielectric film and Ni-YSZ ceramic anode adopt method preparations such as electrochemical deposition (EVD), spraying to form through high temperature sintering usually.The Westinghouse electric corporation was directly used the LSM cathode support afterwards, and supported without CSZ.The main feature of tubular type SOFC is that assembling is simple relatively between battery unit, does not relate to this technical barrier of elevated-temperature seal, becomes extensive battery system than being easier to tandem compound by parallel connection between the battery unit.But tubular type SOFC battery unit preparation technology is quite complicated, needs to adopt electrochemical deposition method, plasma thermal sprayed legal system to be equipped with YSZ dielectric film and bipolar connector usually, and technology of preparing and technology are quite complicated, and raw material availability is low, and cost is very high.
The tubular solid-oxide fuel battery of anode-supported is compared with the tubular solid-oxide fuel battery of cathode support or electrolyte-supported, have the following advantages: because in anode support tube, can form continuous gas cell distribution, so supply of fuel is unrestricted; Because good conductivity is so electric current is steady; And the production cost of this fuel cell is low.
Summary of the invention:
The objective of the invention is to, a kind of preparation method who simplifies the Solid Oxide Fuel Cell manufacturing process and reduce the tubular solid-oxide fuel battery monocell of Solid Oxide Fuel Cell manufacturing cost is provided.
The invention provides a kind of preparation method of tubular solid-oxide fuel battery, comprise the preparation of anode support tube, the finishing of anode support tube, the preparation of dielectric substrate, the preparation of cathode layer, it is characterized in that:
---anode support tube adopts the metal oxide of reducibility and ceramic matric composite to pass through the plasticity extrusion modling;
---prepare the dense electrolyte layer of fuel cell by the method for vacuum-dip-coating.
Among the preparation method of tubular solid-oxide fuel battery of the present invention, the effective pulp bales of described anode-supported is drawn together the pore creating material of 30～60vol% metal oxide, 10～50vol% and the fuel-cell electrolyte mixture of powders of surplus; And will join in the mixture in distilled water, the organic bond of 5～20wt%, the plasticizer of 3～10wt% and the dispersant of 1～7wt% of 15～30wt% of amount of the mixture.
Among the preparation method of tubular solid-oxide fuel battery of the present invention, the finishing of described anode support tube comprises dip-coating, spraying or vacuum-dip-coating.
Among the preparation method of tubular solid-oxide fuel battery of the present invention, described preparation dielectric substrate slurry comprises the electrolyte powder of 5～20wt%, the adhesive of 5～10% dispersant, 1～5 ‰, balance of deionized water.
Among the preparation method of tubular solid-oxide fuel battery of the present invention, wherein prepare negative electrode and adopt the method for brushing.
Specifically, tubular solid-oxide fuel battery single-cell structure of the present invention is supporter with the anode tube, anode tube surface-coated dielectric substrate, and bath surface is brushed negative electrode and is formed monocell.Anode support tube adopts the method preparation of plasticity extruding, utilizes the dielectric substrate of the method for vacuum-dip-coating in the anode support surface preparation densification of modified, through behind the high temperature sintering, coats cathode layer in the dense electrolyte layer surface brush and forms whole monocell.
Described Solid Oxide Fuel Cell, the extrusion modling of anode support tube plasticity, preparation anode support material therefor comprises the electrolyte (as YSZ, the ceria that gadolinium mixes) of Solid Oxide Fuel Cell, and the metal oxide of reducibility.Adopt the vacuum pugging technology, mixing anode-supported body and function compound is with extruder moulding anode support.
When making the tubular solid-oxide fuel battery of anode-supported, the greatest factor that influences production efficiency and production cost is that dielectric substrate is coated to the lip-deep method of anode support tube.Vacuum-dip-coating method that the present invention adopts, this method is simple to operate, and is subjected to the influence of anode shape smaller, does not also need the equipment of exceptional price costliness.
The dielectric substrate of described Solid Oxide Fuel Cell adopts the method preparation of vacuum-dip-coating.Dielectric substrate will follow anode in conjunction with firm, and thin and fine and close, reduces interface impedance, growth three-phase reaction interface between electrode and the electrolyte.Before the preparation dielectric substrate, the antianode supporter is modified and handled is very important, comprises the preroast (600～1100 ℃) of antianode stay pipe, the modification processing on antianode surface.
Described tubular solid-oxide fuel battery prepares before the electrolyte, and the modification cermet material on antianode surface comprises the solid-oxide fuel battery electrolyte and the reducibility metal oxide mixture of different grain size, different content.
The preparation of described tubular solid-oxide fuel battery cathode layer, adopting in the bath surface brushing is the cathode slurry of bonding agent with cellulose (MC).
The preparation method of anode support tube type solid oxide fuel battery of the present invention is used in the Solid Oxide Fuel Cell of various tubuloses, comprises the preparation of the Solid Oxide Fuel Cell of pipe, flat tube and Taper Pipe shape.
Description of drawings:
Fig. 1 is the SEM figure that constitutes electrolyte YSZ of the present invention;
Fig. 2 is the section SEM figure of the single fuel cell of the present invention.
Embodiment:
Below in conjunction with embodiment and accompanying drawing the present invention is done detailed description further, but the scope of protection of present invention is not limited to the scope that execution mode is represented.
Embodiment 1
With NiO powder, YSZ powder (8%mol Y
2O
3Stable ZrO
2, NiO/YSZ mol ratio 1: 1), dispersant, binding agent and solvent, after mixing, adopt the vacuum pugging technology, fully mix, with extruder extrusion modling anode tube.Drying at room temperature, after 1100 ℃ of calcination process, the method that adopts dip-coating is at the powder of anode-supported external surface coating with anode support same material, same composition, diameter of particle 0.5-1.5 μ m.After the drying, on decorative layer, adopt vacuum-dip coating to prepare the YSZ dielectric film, the pipe of gained 1450 ℃ of sintering 2 hours, is obtained the compacted zone of YSZ dielectric film, thickness is about 10 μ m.
Adopt the method preparation (La that brushes
0.8Sr
0.2MnO
3) the LSM/YSZ mixed-powder slurry and contain La
0.6Sr
0.4Co
0.2Fe
0.8O
3The slurry of powder is coated on the electrolyte, obtains the unit Solid Oxide Fuel Cell of whole tubulose after the roasting.
Embodiment 2
Only be the modification processing method of anode-supported tube-surface as different from Example 1, carry out two-layer modification, the ground floor coating is with the powder (NiO/YSZ mol ratio 1: 1) of anode support same material, same ratio, the particle diameter of powder is 0.5-1.5 μ m, after the drying, apply another layer NiO/YSZ powder (weight ratio 3: 7) again, the particle diameter of powder is 0.1-0.5 μ m, and thickness is 1-5 μ m.
With hydrogen is fuel gas, and air is an oxidant, carries out battery performance test at 600-800 ℃, and open circuit voltage slightly improves than the battery of embodiment 1 under uniform temp, and peak power output improves 30%.
Embodiment 3
Only for the electrolyte of Solid Oxide Fuel Cell is the ceria (SDC) that samarium mixes, the cathode material that is adopted is Sm as different from Example 2
0.5Sr
0.5CoO
3
Claims (5)
1. the preparation method of a tubular solid-oxide fuel battery comprises the preparation of anode support tube, the finishing of anode support tube, the preparation of dielectric substrate, the preparation of cathode layer, it is characterized in that:
---anode support tube adopts the metal oxide of reducibility and ceramic matric composite to pass through the plasticity extrusion modling;
---prepare the dense electrolyte layer of fuel cell by the method for vacuum-dip-coating.
2. according to the preparation method of the described tubular solid-oxide fuel battery of claim 1, it is characterized in that: the effective pulp bales of described anode-supported is drawn together the pore creating material of 30～60vol% metal oxide, 10～50vol% and the fuel-cell electrolyte mixture of powders of surplus; And will join in the mixture in distilled water, the organic bond of 5～20wt%, the plasticizer of 3～10wt% and the dispersant of 1～7wt% of 15～30wt% of amount of the mixture.
3. according to the preparation method of the described tubular solid-oxide fuel battery of claim 1, it is characterized in that: the finishing of described anode support tube comprises dip-coating, spraying or vacuum-dip-coating.
4. according to the preparation method of the described tubular solid-oxide fuel battery of claim 1, it is characterized in that: described preparation dielectric substrate slurry, the electrolyte powder that comprises 5～20wt%, the adhesive of 5～10 ‰ dispersant, 1～5 ‰, balance of deionized water.
5. according to the preparation method of the described tubular solid-oxide fuel battery of claim 1, it is characterized in that: wherein prepare negative electrode and adopt the method for brushing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101349462A CN101207218A (en) | 2006-12-22 | 2006-12-22 | Method for preparation of tubular solid-oxide fuel battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101349462A CN101207218A (en) | 2006-12-22 | 2006-12-22 | Method for preparation of tubular solid-oxide fuel battery |
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| CN101207218A true CN101207218A (en) | 2008-06-25 |
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|---|---|---|---|
| CNA2006101349462A Pending CN101207218A (en) | 2006-12-22 | 2006-12-22 | Method for preparation of tubular solid-oxide fuel battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450396A (en) * | 2016-11-15 | 2017-02-22 | 东莞市联洲知识产权运营管理有限公司 | Preparation method of tubular high-temperature solid oxide fuel cells |
| CN108123149A (en) * | 2016-11-25 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of tubular solid oxide fuel cells and preparation method thereof |
| CN108292769A (en) * | 2015-10-08 | 2018-07-17 | 低排放资源公司 | The tubular solid-oxide electrochemical cell of electrode supporting |
-
2006
- 2006-12-22 CN CNA2006101349462A patent/CN101207218A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108292769A (en) * | 2015-10-08 | 2018-07-17 | 低排放资源公司 | The tubular solid-oxide electrochemical cell of electrode supporting |
| CN106450396A (en) * | 2016-11-15 | 2017-02-22 | 东莞市联洲知识产权运营管理有限公司 | Preparation method of tubular high-temperature solid oxide fuel cells |
| CN108123149A (en) * | 2016-11-25 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of tubular solid oxide fuel cells and preparation method thereof |
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