CN1209844C - Single-cell structure of tubelike high-temp. solid oxide fuel battery - Google Patents
Single-cell structure of tubelike high-temp. solid oxide fuel battery Download PDFInfo
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- CN1209844C CN1209844C CNB031145620A CN03114562A CN1209844C CN 1209844 C CN1209844 C CN 1209844C CN B031145620 A CNB031145620 A CN B031145620A CN 03114562 A CN03114562 A CN 03114562A CN 1209844 C CN1209844 C CN 1209844C
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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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Abstract
The present invention discloses a single battery structure of a tubular high temperature solid-oxide fuel battery. The single battery of the tubular high temperature solid-oxide fuel battery is provided with a closed end and an open end, the innermost layer of the single battery is a porous metal ceramic support layer, and the outside of the support layer also comprises at least an anode layer, an electrolyte layer and a cathode layer. The single battery structure of the tubular high temperature solid-oxide fuel battery has the outstanding characteristics that the support layer is adopted, the manufacturing cost of fuel batteries is reduced, and the thermal stress between layers in the battery, especially between electrolyte layers, is relaxed.
Description
Technical field
The invention belongs to the energy, materials processing, power domain, relate to the fuel cell structure, particularly a kind of structure of tubular high temperature solid oxide fuel cell monocell.
Background technology
Fuel cell is the Blast Furnace Top Gas Recovery Turbine Unit (TRT) that a kind of chemical energy with fuel is directly changed into electric energy.Wherein Solid Oxide Fuel Cell (SOFC) is considered to the third generation Blast Furnace Top Gas Recovery Turbine Unit (TRT) after phosphate type fuel battery (PAFC) and molten carbonate fuel cell (MCFC).It is about 50% that the generating efficiency of Solid Oxide Fuel Cell 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%.
At present, the structure of the high temperature solid oxide fuel cell of exploitation mainly contains tabular and two kinds of structures of tubulose in the world.Platy structure has that current channel is short, output current density and advantages such as power density height and battery pile compactness, has the elevated-temperature seal difficulty simultaneously, elevated temperature heat stress technical barrier such as do not match; Tubular structure has the elevated-temperature seal of need not, thermal stress is less and the monocell assembling is simple, easily realizes characteristics such as high-power.
So far, the representative producer of exploitation tubular structure mainly contain the Westinghouse Electrical Corp. (Westinghouse E1ectric Crop.) of the U.S. and Japanese Mitsubishi Heavy Industries Ltd (Mitsubishi HeavyIndustries, Lts.).Wherein to have related to a kind of be the structure of supporting layer with the dielectric substrate to CN1277096; EP0055016 and US5108850 have related to the structure of cathode layer as supporting layer.
Summary of the invention
The objective of the invention is to, a kind of structure that adopts metal ceramic tube as the tubular high temperature solid oxide fuel cell monocell of supporting layer is provided, this structure possess tubular SOFC need not the assembling of elevated-temperature seal, battery simple, be easy to realize advantage such as high-power, and make it on performance, have the characteristics of tabular SOFC High Output Current density and power density concurrently.
Realize that technical scheme of the present invention is, the structure of this tubular high temperature solid oxide fuel cell monocell, this structure is end sealing, one end opening, be characterized in, the supporting layer that the structure innermost layer is made with the metal ceramic tube of porous, in effective power generation region of structure, its supporting layer at least also comprises anode layer, dielectric substrate, cathode layer and the negative electrode of the fuel cell layer that confluxes outward.
Some other characteristics of the present invention are:
The metal ceramic tube supporting layer of described porous is a structure sheaf of battery structure, by other structure sheaf of metal ceramic tube support layer supports battery, and the double as anode layer that confluxes.
The material selection pottery of described porous metalloceramic supporting layer is with the compound of metal or mix the cermet material that constitutes.
Metal in the described porous metalloceramic supporting layer is maintained fixed content with the relative amount of pottery in whole coating, or in coating, change, make that the coefficient of linear expansion and the dielectric substrate of metal ceramic tube are suitable, the structure sheaf cracking that causes with the difference that prevents because of coefficient of linear expansion makes the step-down of battery delivery efficiency.
The material of described porous metalloceramic supporting layer, its ceramic material is selected from one or more in silica, aluminium oxide, mullite, cordierite, carborundum, molybdenum silicide, zirconium boride, titanium boride, tungsten carbide, the titanium oxide, and its metal material is selected from one or more in cheap metallic nickel, iron, chromium, chromium-base alloy, nickel-base alloy, the ferrous alloy.
Described supporting layer, anode layer, dielectric substrate, cathode layer, the negative electrode non-conterminous every two-layer needs that conflux in the layer are isolated effectively.
Described porous metalloceramic supporting layer is positioned at the open end of monocell, the effective power generation region that is structure can be a coating layer outward, the material of this coating layer can be the anode material of fuel cell, or is metal, pottery or the cermet of the high conductivity different with anode material.
Described coating layer is as the lead portion of anode current.
The structure of the tubular high temperature solid oxide fuel cell monocell that the present invention adopts, can regulate the ratio of the thickness and the cermet material of cermet stay pipe easily, the structure sheaf cracking that makes the coefficient of linear expansion of metal ceramic tube and dielectric substrate quite cause with the difference that prevents because of coefficient of linear expansion makes the step-down of battery delivery efficiency; The metal ceramic tube that the present invention adopts also can be taken into account anode and conflux, and improves conductive capability, and can reduce manufacturing cost.The metal material of preparation metal ceramic tube can be selected cheap metal, as nickel, iron, chromium, can also select the metal alloy of ferronickel chromium base, as chromium-base alloy, nickel-base alloy, ferrous alloy; Ceramic material can selective oxidation thing pottery or compound oxidate ceramic, as silica, titanium oxide, aluminium oxide, mullite, cordierite, can select the carbide ceramics material, as carborundum, tungsten carbide, can select silicide ceramics, as molybdenum silicide, can select boride ceramics, as zirconium boride, titanium boride, can select nitride ceramics, as silicon nitride.
Description of drawings
Fig. 1 is a kind of tubular high temperature solid oxide fuel cell single-cell structure generalized section;
Fig. 2 has only listed the conflux A-A profile of layer structure of three kinds of different negative electrodes;
Fig. 3 is the B-B profile of Fig. 1.
Embodiment
The specific embodiment that provides below in conjunction with accompanying drawing and inventor is described in further detail the present invention.
Fig. 1 is a kind of tubular high temperature solid oxide fuel cell single-cell structure generalized section, and Fig. 2 has only listed the conflux A-A profile of layer structure of three kinds of different negative electrodes, and Fig. 3 is the B-B profile of Fig. 1.
As shown in Figure 1, the structure of this monocell 1 is an end opening, the tubular structure of end sealing.Its innermost layer is the supporting layer 2 of fuel cell, in effective generating length, and anode layer 3, dielectric substrate 4, cathode layer 5 and the negative electrode that its supporting layer the is followed successively by fuel cell outward layer 6 that confluxes.
Some is not covered the openend of monocell as shown in Figure 1 by dielectric substrate, but on supporting layer 2, prepared coating layer 7, the material of coating layer 7 can be the anode material of fuel cell, also can be metal, pottery or the cermet material of other high conductivity.Coating layer 7 parts can be used as the lead portion of anode current.The generalized section of coating layer 7 as shown in Figure 3.
The supporting layer 2 of above-mentioned monocell is the cermet structure of porous, and described cermet is the compound or composite material of metal and pottery, wherein pottery can selective oxidation aluminium, in the multiple potteries such as titanium oxide and zirconia one or more; Wherein metal can be selected one or more in the multiple metals such as nickel, nickel-base alloy and chromium.Control the ratio of two class materials and the thermal coefficient of expansion of thermal coefficient of expansion and dielectric substrate and coincide, and will take into account the effect of confluxing of antianode; The thickness of cermet stay pipe is for O.2mm-4mm, the supporting layer of monocell radial thickness in the axial direction can be constant, also can the characteristics of current density change in gradient when battery operated, i.e. radial thickness attenuation successively from the radial thickness of openend to blind end.
The anode layer 3 of above-mentioned monocell is the porous metalloceramic structure, and the volumn concentration of metal is 20%-70% in the cermet.
The dielectric substrate 4 of above-mentioned monocell is a compacted zone, in order to improve monocell efficient, its thickness is less than 100 microns, and dielectric substrate 4 must be effectively separates supporting layer and anode layer and cathode layer and the negative electrode layer that confluxes, promptly can not make conflux arbitrary layer of layer of arbitrary layer and the cathode layer and the negative electrode of supporting layer and anode layer directly contact, in order to avoid cause internal short-circuit of battery.
The negative electrode of above-mentioned monocell confluxes layer 6 can be according to the current density of monocell and negative electrode 5 and negative electrode the conflux conductive capability of the utmost point 6 all covered cathode layer, perhaps part covered cathode layer on monocell cathode layer radial and axial.Negative electrode confluxes the thickness of layer on radial and axial direction can be according to the characteristics of current density, uneven distribution.Fig. 2 has only enumerated the conflux generalized section of layer 6 of three kinds of multi-form negative electrodes.Its cross-sectional profile can be earless shape (Fig. 2-A), monaural shape (Fig. 2-B) and ears shape (Fig. 2-C).
Enforcement of the present invention can be regulated the ratio of the thickness and the cermet material of cermet stay pipe easily, the structure sheaf cracking that makes the coefficient of linear expansion of metal ceramic tube and dielectric substrate quite cause with the difference that prevents because of coefficient of linear expansion makes the step-down of battery delivery efficiency, and metal ceramic tube can be taken into account anode and conflux, and relaxes each interlayer of battery especially and the thermal stress between dielectric substrate.Because adopt metal ceramic tube to support, what its metal and ceramic material can be selected cheapness is main as metallic nickel and aluminium oxide ceramics, can significantly reduce the manufacturing cost of fuel cell.
The structure of high temperature solid oxide fuel cell monocell involved in the present invention only limits to the structure shown in the Figure of description absolutely not.
Claims (8)
1. the structure of a tubular high temperature solid oxide fuel cell monocell, this structure is end sealing, one end opening, it is characterized in that, the structure innermost layer with the metal ceramic tube of porous as supporting layer (2), in effective power generation region of structure, anode layer (3), dielectric substrate (4), cathode layer (5) and the negative electrode that its supporting layer (2) is outer at least also to comprise fuel cell conflux layer (6).
2. the structure of tubular high temperature solid oxide fuel cell monocell according to claim 1, it is characterized in that, the metal ceramic tube supporting layer (2) of described porous is a structure sheaf of battery structure, by other structure sheaf of metal ceramic tube supporting layer (2) support cells, and the double as anode layer that confluxes.
3. the structure of tubular high temperature solid oxide fuel cell monocell according to claim 1 and 2 is characterized in that, the material selection pottery of described porous metalloceramic supporting layer (2) is with the compound of metal or mix the cermet material that constitutes.
4. the structure of tubular high temperature solid oxide fuel cell monocell according to claim 1, it is characterized in that, metal in the described porous metalloceramic supporting layer (2) is maintained fixed content with the relative amount of pottery in whole coating, or in coating, change, make that the coefficient of linear expansion and the dielectric substrate of metal ceramic tube are suitable, the structure sheaf cracking that causes with the difference that prevents because of coefficient of linear expansion makes the step-down of battery delivery efficiency.
5. the structure of tubular high temperature solid oxide fuel cell monocell according to claim 3, it is characterized in that, the material of described porous metalloceramic supporting layer (2), its ceramic material is selected from one or more in silica, aluminium oxide, mullite, cordierite, carborundum, molybdenum silicide, zirconium boride, titanium boride, tungsten carbide, the titanium oxide, and its metal material is selected from one or more in cheap metallic nickel, iron, chromium, chromium-base alloy, nickel-base alloy, the ferrous alloy.
6. the structure of tubular high temperature solid oxide fuel cell monocell according to claim 1, it is characterized in that, described supporting layer (2), anode layer (3), dielectric substrate (4), cathode layer (5), negative electrode conflux the layer (6) in non-conterminous every two-layer needs isolate effectively.
7. the structure of tubular high temperature solid oxide fuel cell monocell according to claim 1, it is characterized in that, the open end preparation that described porous metalloceramic supporting layer (2) is positioned at monocell has coating layer (7), the material of this coating layer (7) is the anode material of fuel cell, or the metal of the high conductivity different with anode material, pottery or cermet.
8. the structure of tubular high temperature solid oxide fuel cell monocell according to claim 6 is characterized in that, described coating layer (7) is as the lead portion of anode current.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031145620A CN1209844C (en) | 2003-03-21 | 2003-03-21 | Single-cell structure of tubelike high-temp. solid oxide fuel battery |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB031145620A CN1209844C (en) | 2003-03-21 | 2003-03-21 | Single-cell structure of tubelike high-temp. solid oxide fuel battery |
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| CN1438723A CN1438723A (en) | 2003-08-27 |
| CN1209844C true CN1209844C (en) | 2005-07-06 |
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| CNB031145620A Expired - Fee Related CN1209844C (en) | 2003-03-21 | 2003-03-21 | Single-cell structure of tubelike high-temp. solid oxide fuel battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111403763A (en) * | 2020-03-31 | 2020-07-10 | 西安交通大学 | Metal thin-wall tube supporting type micro-tube solid oxide fuel cell and cell stack structure |
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| CN100403591C (en) * | 2003-10-20 | 2008-07-16 | 中国科学院过程工程研究所 | Structure of tube still type solid oxide electrolyte high-temperature gas electrolyzer |
| JP4935054B2 (en) * | 2005-11-10 | 2012-05-23 | トヨタ自動車株式会社 | Tube fuel cell and method for manufacturing the same |
| JP5040097B2 (en) * | 2005-11-10 | 2012-10-03 | トヨタ自動車株式会社 | Tube type fuel cell module |
| CN100365859C (en) * | 2006-03-21 | 2008-01-30 | 西安交通大学 | Structure of tubular high temperature solid oxide fuel cell single tube battery pack |
| CN101719554B (en) * | 2009-12-08 | 2012-02-29 | 中国科学院过程工程研究所 | Test tube type mesothermal solid-oxide fuel cell |
| CN102306818B (en) * | 2011-08-23 | 2013-12-11 | 西安交通大学 | Tubular solid oxide fuel cell stack structure and preheating method thereof |
| CN103872366B (en) * | 2012-12-12 | 2016-12-07 | 中国科学院上海硅酸盐研究所 | A kind of metal-supported solid oxide fuel cell and preparation method thereof |
| CN105161743B (en) * | 2015-10-14 | 2018-01-30 | 中国科学院宁波材料技术与工程研究所 | A kind of anode and stack unit of high-temperature solid fuel cell |
| CN110190210B (en) * | 2019-03-12 | 2024-05-24 | 华电电力科学研究院有限公司 | Solid oxide fuel cell structure convenient for edge sealing |
| CN110890571B (en) * | 2019-11-19 | 2021-05-28 | 西安交通大学 | Tubular solid oxide fuel cell with double-layer connecting electrodes connected in series |
| CN110890570B (en) * | 2019-11-19 | 2021-05-28 | 西安交通大学 | Preparation method of tubular solid oxide fuel cell with double-layer connecting electrodes connected in series |
| CN111403762B (en) * | 2020-03-31 | 2021-05-18 | 西安交通大学 | Ceramic and metal common support flat tube, battery/electrolytic cell and battery stack structure |
| CN114122471B (en) * | 2021-11-26 | 2023-12-19 | 江苏科技大学 | Methanol solid oxide fuel cell and power generation system comprising same |
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2003
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111403763A (en) * | 2020-03-31 | 2020-07-10 | 西安交通大学 | Metal thin-wall tube supporting type micro-tube solid oxide fuel cell and cell stack structure |
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