CN1655386A - Method for connecting ceramal in solid oxide fuel battery - Google Patents
Method for connecting ceramal in solid oxide fuel battery Download PDFInfo
- Publication number
- CN1655386A CN1655386A CNA2005100631442A CN200510063144A CN1655386A CN 1655386 A CN1655386 A CN 1655386A CN A2005100631442 A CNA2005100631442 A CN A2005100631442A CN 200510063144 A CN200510063144 A CN 200510063144A CN 1655386 A CN1655386 A CN 1655386A
- Authority
- CN
- China
- Prior art keywords
- ceramic
- metal
- pottery
- connector
- oxide fuel
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000007787 solid Substances 0.000 title claims abstract description 20
- 239000000446 fuel Substances 0.000 title claims description 24
- 239000000919 ceramic Substances 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- 238000001465 metallisation Methods 0.000 claims abstract description 18
- 239000007769 metal material Substances 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000004519 grease Substances 0.000 claims abstract description 5
- 238000005498 polishing Methods 0.000 claims abstract description 4
- 238000003466 welding Methods 0.000 claims abstract description 4
- 238000007789 sealing Methods 0.000 claims description 21
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000956 alloy Substances 0.000 claims description 17
- 239000003792 electrolyte Substances 0.000 claims description 15
- 229910045601 alloy Inorganic materials 0.000 claims description 14
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 7
- 239000010445 mica Substances 0.000 claims description 7
- 229910052618 mica group Inorganic materials 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011224 oxide ceramic Substances 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 230000006641 stabilisation Effects 0.000 claims description 6
- 238000011105 stabilization Methods 0.000 claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 238000005476 soldering Methods 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 229910017060 Fe Cr Inorganic materials 0.000 claims description 4
- 229910002544 Fe-Cr Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 230000000295 complement effect Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000007747 plating Methods 0.000 claims description 4
- 229910000838 Al alloy Inorganic materials 0.000 claims description 3
- 229910000599 Cr alloy Inorganic materials 0.000 claims description 3
- 229910017309 Mo—Mn Inorganic materials 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- -1 carbon silicon titanium-aluminium Chemical compound 0.000 claims description 3
- 239000011195 cermet Substances 0.000 claims description 3
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- 239000002344 surface layer Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 229910000679 solder Inorganic materials 0.000 abstract 1
- 239000003566 sealing material Substances 0.000 description 10
- 238000005275 alloying Methods 0.000 description 8
- 230000035882 stress Effects 0.000 description 7
- 230000006378 damage Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 239000006071 cream Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000008646 thermal stress Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002241 glass-ceramic Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910008423 Si—B Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000011712 cell development Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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
Abstract
This invention provides a solid oxidation cell metal material and ceramics connection method, which comprises the following steps: metallization processing on the ceramic surface; coating metal layer on the ceramic metal surface; grinding and polishing the metal layer and removing grease and dirt; welding the ceramics and the metal materials through fiber solder; after welding, adopting the cooling speed of 20Deg. C /min-25Deg. C /min and cooling down in air below the temperature of 300 degrees.
Description
Technical field the present invention relates to metal material and ceramic high temperature method of attachment in a kind of Solid Oxide Fuel Cell (SOFC).
The Solid Oxide Fuel Cell of background technology plate armature is owing to the power density height, and production cost is low, is the emphasis of present Solid Oxide Fuel Cell development.In the flat solid oxide fuel cell structure, the three-in-one structure that electrolyte both sides composite cathode and anode constitute is called as battery unit, by seal, sealing materials battery unit and the metallic interconnect materials that has gas passage are combined, repeat to form Solid Oxide Fuel Cell series-connected cell heap successively.The working temperature of battery pile is 600-1000 ℃, and the reliability of seal, sealing materials and sealing technology can guarantee that the safety of fuel gas and oxidizing gas is isolated among the SOFC, guarantees the operate as normal of SOFC.
Because the difference between the hot expansibility among the SOFC between the different group element materials, in the SOFC course of work and in many loop start processes of SOFC, the stress of existence can cause the destruction of link weak link.Seal, sealing materials partly is the main concentration zones of stress, therefore destroys mainly concentrating on the seal, sealing materials place; Owing to electrolyte among the SOFC is thinner, be generally the 20-200 micron in addition, therefore also be easy to damage.Above-mentioned any one destruction all can cause whole SOFC to lose function.
Lu's Zhe, Su Wenhui (application number: 99104482, publication number: 1234617) with Al
2O
3, SiO
2, CAO etc. is raw material, sealing-in ceramic powder and outer sealing-in vitreous material in making have been implemented the high intermediate temperature sealing of Solid Oxide Fuel Cell.Dong Yong comes, journey plan outstanding person (application number: 02124834, publication number: 1465647) with the ceramic glaze of fusion as sealant, as the sealing supporter, prepared the encapsulant of Solid Oxide Fuel Cell with powder body materials such as zirconia, titanium oxide, silica, aluminium oxide.Han Minfang, Peng Suping (application number: 02147179, publication number: 1469497) oxide with CA-Mg-Fe-Si-B-Zr-Y is a key component, has realized the high intermediate temperature sealing of Solid Oxide Fuel Cell (SOFC).Zheng Rui, Wen Tinglian (application number: 03150698, publication number: 1494176) adopt CA-Al-Si-B system oxide devitrified glass to prepare a series of encapsulants that are applicable to 800～1000 ℃, realized flat solid oxide fuel cell (SOFC) in high intermediate temperature sealing.
All these methods all are to seek a kind ofly can to form the method that is tightly linked between Zirconia electrolytic and metal union body, and the seal, sealing materials of all uses all belongs to the category of glass ceramics, are the methods of generally using in the present SOFC sealing-in.
Though above-mentioned method for sealing can both be realized the sealing between the electrolyte and union body among the flat SOFC, because the glass sealing material is bad to the wetability of metal, often cause sealing strength not enough, or air-tightness is not enough.SOFC is operated in the 600-1000 ℃ of scope, also often need circulate to the startup between the working temperature in room temperature.Because the difference between Zirconia electrolytic and the thermal coefficient of expansion of metal union body different materials own will form thermal stress like this between electrolyte, seal, sealing materials and union body.The destruction that thermal stress causes can at first appear at the weak link among the three: electrolyte and seal, sealing materials.Will influence the life-span of SOFC like this.
Liu Jiang, Su Wenhui (application number: 02133049, publication number: 1414646) the use silver metal conducting resinl of Ti Chuing carries out the method for solid oxide fuel cell fast sealing, has also realized the electrolyte of fuel cell or the sealing-in between device and other members.Make seal, sealing materials with silver conductive adhesive, can guarantee all have adhesion strength between good air-tightness and device at high-temperature region and low-temperature space, seal, sealing materials adheres to well, chemical property stable and thermal stress is low.But silver conductive adhesive also exists serviceability temperature on the low side, the problem of the bad solution of insulating properties.
Summary of the invention is at problems of the prior art, in order to realize many loop start work of SOFC, also in order to prolong the working life of SOFC, the present invention proposes a kind of novel method of attachment in flat SOFC, i.e. method by at first metallizing and be connected with metal connector at ceramic surface.This method is specially adapted to alloy metallic interconnect materials and ceramic being connected in the Solid Oxide Fuel Cell (SOFC), but is not limited to Solid Oxide Fuel Cell, can also be used for being connected of other similar pottery and metal.
In some SOFC structures, need be connected with ceramic material metal material.The invention provides being connected and method of attachment of metal material in the structure of a kind of SOFC and ceramic material.Method of the present invention is particularly suited for following SOFC structure.In SOFC, electrolyte is thin more, and the inside battery loss is just few more, wishes that therefore electrolyte gets over Bao Yuehao.But electrolyte is thin more, and its mechanical property is just low more, is easy to damage, and finally causes whole SOFC to lose efficacy.In order to solve this contradiction, the inventor has proposed to add the battery structure that one deck ceramic supporting body forms between alloy connector and thin-film electrolyte, for example in the disclosed Solid Oxide Fuel Cell structure of CN1555105A, wherein select a kind of ceramic material that is complementary with the electrolyte hot expansibility for use, can the two link together with it by the method for sealing of routine or the glass ceramics method for sealing that is provided in the CN1469497A patent of invention by the inventor, and then ceramic support and alloy connector are linked together by the method that the present invention proposes.So both guaranteed in SOFC, can adopt very thin electrolyte, guaranteed again that it was not by the stress rupture in the sealing-in.
In above-mentioned SOFC structure, the preferred supporter pottery that is complementary with the Zirconia electrolytic hot expansibility that uses is implemented to be connected with the alloy connector.Preferred supporter pottery has yttria-stabilized zirconia (YSZ), cubic stabilization zirconium oxide ceramic (TZP), partial stabilization zirconium oxide ceramic (PSZ), mica ceramics, Zirconia reinforced alumina ceramic (ZTA) etc.
Preferred metallic interconnect materials is low-expansion alloy material or cermet material, and for example the Fe-Cr ferritic stainless steel can cut down controlled expansion alloy, comprise in the fe-cr alloy that as 4J28, iron-nickel is that 4J42,4J43, Fe-Ni-Cr-are 4J6,4J24,4J46 etc., carbon silicon titanium-aluminium alloy belongs to pottery.MODIFIED Fe-Cr the ferritic stainless steel (HLFeCr18) of special recommendation preparation in the CN1468970A invention.
The invention provides following concrete technical scheme:
(1) a kind of metal material in Solid Oxide Fuel Cell (SOFC) and ceramic method of attachment may further comprise the steps:
Carry out metalized at ceramic surface;
At ceramic metallization plating metal on surface layer;
After polishing, polish at layer on surface of metal, remove grease and dirt;
By soldering together with pottery and Metal Material Welding;
After joint has welded, preferably adopt the cooling rate of 20 ℃/min～25 ℃/min to cool off, can come out of the stove, in air, cool off when being cooled to not to be higher than 300 ℃ with stove.
(2) according to the method for above-mentioned (1), wherein, described metal material is the connector of oxide fuel cell.
(3) according to the method for claim (1) or (2), wherein, described Solid Oxide Fuel Cell is included in the ceramic supporting body between metal material connector and the thin-film electrolyte.
(4) according to the method for above-mentioned (3), wherein, described Solid Oxide Fuel Cell comprises repeated arrangement connector, ceramic supporting body, glass to ceramic seal circle, cell, glass to ceramic seal circle, ceramic supporting body, connector successively ...
(5) according to arbitrary method in above-mentioned (1)-(4), wherein, activation Mo-Mn method is adopted in described metallization, can adopt following composition Mo 60-75%, Mn 6-12%, Al
2O
38-15%, SiO
26-10%, CaO 0.5-2%, the preferred employing following the composition, by weight percentage, Mo 70%, and Mn 9%, Al
2O
312%, SiO
28%, CaO 1%.
(6) according to arbitrary method in claim (1)-(5), wherein, the described coat of metal is a nickel dam.
(7) according to arbitrary method in claim (1)-(6), wherein, adopt and implement ways of connecting simultaneously in the both sides, metal surface, promptly form Ceramic-to-Metal-ceramic structure, all put pottery in the metal connector both sides.
(8) according to arbitrary method in claim (1)-(7), wherein, when pottery and alloy connector being welded together, preferably adopt the Ag scolder by soldering, sealing temperature is 1000 ℃, is incubated 5 minutes.
(9) according to arbitrary method in claim (1)-(8), wherein, described supporter adopts the supporter pottery that is complementary with the Zirconia electrolytic hot expansibility, for example yttria-stabilized zirconia (YSZ), cubic stabilization zirconium oxide ceramic (TZP), partial stabilization zirconium oxide ceramic (PSZ), mica ceramics, Zirconia reinforced alumina ceramic (ZTA).
(10) according to arbitrary method in claim (1)-(9), wherein, connector adopts low-expansion alloy material or cermet material to make, for example the Fe-Cr ferritic stainless steel can cut down controlled expansion alloy, in the fe-cr alloy as 4J28, iron-nickel is that 4J42,4J43, Fe-Ni-Cr-are 4J6,4J24,4J46, and carbon silicon titanium-aluminium alloy belongs to pottery.
Embodiment
In a specific embodiments, implement pottery among the present invention and mainly be divided into following steps with the metal sealing method:
1. adopt activation Mo-Mn method to carry out metalized one time at ceramic surface;
2. at ceramic metallization plating metal on surface nickel dam;
3. after the metal surface polishes, polishes, take acid wash to remove grease and dirt.
4. implement sealing-in simultaneously in the both sides, metal surface.Be Ceramic-to-Metal-pottery, promptly the method for sealing of pottery is all put in the metal both sides, makes residual stress two face balances, to reduce the residual stress of single side.
5. by soldering pottery and alloy connector are welded together.Ag scolder, sealing temperature: 1000 ℃, be incubated 5 minutes are adopted in sealing-in.
6. after joint has welded, cool off with stove, can come out of the stove, in air, cool off when being cooled to 300 ℃ with the cooling rate of 20 ℃/min～25 ℃/min.
7. the good device of sealing-in is hunted leak, checked its air-tightness.
Embodiment 1:YSZ pottery is connected with the HLFeCr18 alloying metalization
Metallization powder and prescription thereof:
Metallize all raw materials and prescription thereof is metallized key.Among the present invention, adopt metallizing formula following (percentage by weight is formed wt%):
Mo Mn Al
2O
3 SiO
2 CaO
60-75 6-12 8-15 6-10 0.5-2
Preferred metallizing formula following (percentage by weight is formed wt%):
Mo Mn Al
2O
3 SiO
2 CaO
70 9 12 8 1
The granularity of metallization powder wants thin, is generally 2～3 μ m, and main body is refractory metal Mo and Mn, and activator has SiO
2, CaO, Al
2O
3Deng.SiO
2Be to improve wettability, Al
2O
3Be to improve metallized intensity.
The coating of cream is joined in metallization:
With raw materials used in the metallizing formula, in glass jar, mixed tens of hours after the careful weighing, take out the back and add an amount of diethy-aceto oxalate, after treating all to soak into, put into the super 20min of ultrasonic wave again, add a certain amount of guncotton solution then, to form the paste of certain viscosity.
Be coated with cream can be by hand pen be coated with, machinery is coated with, spray gun sprays and silk screen printing etc., the inconsistent experiment product of size should be coated with pen for quantity is few; And, then should use silk screen printing for the large-scale production of identical product.Being coated with cream thickness must be even, and THICKNESS CONTROL is advisable at 30～100 μ m usually, and preferred thickness is 40～50 μ m.
The metallization sintering process:
Coat the porcelain spare oven dry back sintering of paste.Sintering can carry out in vertical or horizontal hydrogen stove.Working gas can be pure hydrogen, also H can be arranged
2, N
2Gaseous mixture, but no matter what gas all should be taked wet hydrogen when the metallization sintering, general dew point is advisable with 10～30 ℃.Usually metallizing temperature is 1300～1550 ℃, and temperature retention time is 20～60min.Preferred metallizing temperature is 1350～1450 ℃, and temperature retention time is 30～40min.
At the ceramic metallized layer plating nickel on surface, thickness of coating is 10-50 μ m, preferred 15-25 μ m.
The sealing-in metal adopts the MODIFIED Fe-Cr ferritic stainless steel (called after HLFeCr18) of preparation in the CN1468970A invention, and its thermal coefficient of expansion is 12 * 10
-6/ K.After Fe-Cr alloying metal surface rubbing, the polishing, take acid wash to remove grease and dirt.Implement sealing-in simultaneously in the both sides, metal surface.
When implementing metal sealing, adopt balance method, i.e. Ceramic-to-Metal-pottery, promptly the method for sealing of pottery is all put in the metal both sides, makes residual stress two face balances, to reduce the residual stress of single side.
When implementing metal sealing, preferably be processed into the thin metal band of projection in the metal surface, width 0.5-2mm highly is 0.2-1mm.
When implementing metal sealing, Ag scolder, sealing temperature: 1000 ℃, be incubated 5 minutes are adopted in sealing-in.
After joint has welded, cool off with stove with the cooling rate of 20 ℃/min～25 ℃/min, can not be too fast.Can come out of the stove when being cooled to 300 ℃, in air, cool off.
Use the helium mass-spectrometer leak detector that the good device of sealing-in is hunted leak, vacuum degree is 10
-11Atm.Show that said method can realize that air-tightness is connected between YSZ electrolyte and the HLFeCr18 alloy.
Example 2:TZP pottery is connected with the HLFeCr18 alloying metalization
Adopt the YSZ pottery in the TZP pottery alternative embodiment 1, carry out the TZP pottery and be connected with the HLFeCr18 alloying metalization.The final helium mass-spectrometer leak detector that uses is hunted leak to the good device of sealing-in, and vacuum degree is 10
-11Atm.Show that said method can realize that air-tightness is connected between TZP pottery and the HLFeCr18 alloy.
Example 3:ZTA pottery is connected with the HLFeCr18 alloying metalization
Adopt the YSZ pottery in the ZTA pottery alternative embodiment 1, carry out the ZTA pottery and be connected with the HLFeCr18 alloying metalization.The final helium mass-spectrometer leak detector that uses is hunted leak to the good device of sealing-in, and vacuum degree is 10
-11Atm.Show that said method can realize that air-tightness is connected between ZTA pottery and the HLFeCr18 alloy.
Example 4: mica ceramics is connected with the HLFeCr18 alloying metalization
Adopt the YSZ pottery in the mica ceramics alternative embodiment 1, carry out mica ceramics and be connected with the HLFeCr18 alloying metalization.The final helium mass-spectrometer leak detector that uses is hunted leak to the good device of sealing-in, and vacuum degree is 10
-11Atm.Show that said method can realize that air-tightness is connected between mica ceramics and the HLFeCr18 alloy.
Claims (9)
1. metal material in Solid Oxide Fuel Cell (SOFC) and ceramic method of attachment may further comprise the steps:
Carry out metalized at ceramic surface;
At ceramic metallization plating metal on surface layer;
After polishing, polish at layer on surface of metal, remove grease and dirt;
By soldering together with pottery and Metal Material Welding;
After joint has welded, preferably adopt the cooling rate of 20 ℃/min～25 ℃/min to cool off, can come out of the stove, in air, cool off when being cooled to not to be higher than 300 ℃ with stove.
2. according to the process of claim 1 wherein, described metal material is the connector of oxide fuel cell.
3. according to the method for claim 1 or 2, wherein, described oxide fuel cell is included in the ceramic supporting body between metal material connector and the thin-film electrolyte.
4. according to the method for claim 3, wherein, described oxide fuel cell comprises repeated arrangement connector, ceramic supporting body, glass to ceramic seal circle, cell, glass to ceramic seal circle, ceramic supporting body, connector successively ....
According to each method among the claim 1-4, wherein, activation Mo-Mn method is adopted in described metallization, can adopt following composition Mo 60-75%, Mn 6-12%, Al
2O
38-15%, SiO
26-10%, CaO 0.5-2%, the preferred employing following the composition, by weight percentage, Mo 70%, and Mn 9%, Al
2O
312%, SiO
28%, CaO 1%.
5. according to each method among the claim 1-5, wherein, the described coat of metal is a nickel dam.
6. according to each method among the claim 1-6, wherein, adopt and implement ways of connecting simultaneously, promptly form Ceramic-to-Metal-ceramic structure, all put pottery in the metal connector both sides in the both sides, metal surface.
7. according to each method among the claim 1-7, wherein, when pottery and alloy connector being welded together, preferably adopt the Ag scolder by soldering, sealing temperature is 1000 ℃, is incubated 5 minutes.
8. according to each method among the claim 1-8, wherein, described supporter adopts the supporter pottery that is complementary with the Zirconia electrolytic hot expansibility, for example yttria-stabilized zirconia (YSZ), cubic stabilization zirconium oxide ceramic (TZP), partial stabilization zirconium oxide ceramic (PSZ), mica ceramics, Zirconia reinforced alumina ceramic (ZTA).
9. according to each method among the claim 1-9, wherein, connector adopts low-expansion alloy material or cermet material to make, for example the Fe-Cr ferritic stainless steel can cut down controlled expansion alloy, in the fe-cr alloy as 4J28, iron-nickel is that 4J42,4J43, Fe-Ni-Cr-are 4J6,4J24,4J46, and carbon silicon titanium-aluminium alloy belongs to pottery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100631442A CN1319202C (en) | 2005-04-05 | 2005-04-05 | Method for connecting ceramal in solid oxide fuel battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100631442A CN1319202C (en) | 2005-04-05 | 2005-04-05 | Method for connecting ceramal in solid oxide fuel battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1655386A true CN1655386A (en) | 2005-08-17 |
| CN1319202C CN1319202C (en) | 2007-05-30 |
Family
ID=34894612
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100631442A Expired - Fee Related CN1319202C (en) | 2005-04-05 | 2005-04-05 | Method for connecting ceramal in solid oxide fuel battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1319202C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103236513A (en) * | 2013-05-03 | 2013-08-07 | 北京科技大学 | IT-SOFC (Intermediate Temperature Solid Oxide Fuel Cell) stack alloy connecting body and connecting method of cell stack |
| CN103779526A (en) * | 2012-10-25 | 2014-05-07 | 中央大学 | Ceramic metal film, method for producing same and use thereof |
| CN104779406A (en) * | 2015-04-23 | 2015-07-15 | 常州联德电子有限公司 | Forming process of metal connector of solid oxide fuel battery |
| CN113555576A (en) * | 2021-06-22 | 2021-10-26 | 青岛大学 | Fuel cell metal connector coating |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3169796D1 (en) * | 1980-05-23 | 1985-05-15 | Meidensha Electric Mfg Co Ltd | Vacuum-housed circuit interrupter |
| DE4320910C1 (en) * | 1993-06-18 | 1994-09-08 | Siemens Ag | Method of producing a gastight soldered connection and use of this method in the production of components having a vacuum-tight housing |
| AUPP042597A0 (en) * | 1997-11-17 | 1997-12-11 | Ceramic Fuel Cells Limited | A heat resistant steel |
| CN1252844C (en) * | 2003-12-22 | 2006-04-19 | 韩敏芳 | Novel plate assembled solid oxide fuel cell |
-
2005
- 2005-04-05 CN CNB2005100631442A patent/CN1319202C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103779526A (en) * | 2012-10-25 | 2014-05-07 | 中央大学 | Ceramic metal film, method for producing same and use thereof |
| CN103779526B (en) * | 2012-10-25 | 2016-05-11 | 中央大学 | Ceramic metal film, method for producing same and use thereof |
| CN103236513A (en) * | 2013-05-03 | 2013-08-07 | 北京科技大学 | IT-SOFC (Intermediate Temperature Solid Oxide Fuel Cell) stack alloy connecting body and connecting method of cell stack |
| CN103236513B (en) * | 2013-05-03 | 2015-06-03 | 北京科技大学 | IT-SOFC (Intermediate Temperature Solid Oxide Fuel Cell) stack alloy connecting body and connecting method of cell stack |
| CN104779406A (en) * | 2015-04-23 | 2015-07-15 | 常州联德电子有限公司 | Forming process of metal connector of solid oxide fuel battery |
| CN113555576A (en) * | 2021-06-22 | 2021-10-26 | 青岛大学 | Fuel cell metal connector coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1319202C (en) | 2007-05-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10658684B2 (en) | Sanbornite-based glass-ceramic seal for high-temperature applications | |
| CN102386345B (en) | Sealing gasket for medium-and-low temperature solid oxide fuel cell, and manufacturing method and application of sealing gasket | |
| CN102084530B (en) | Non-contaminating, electro-chemically stable glass frit sealing materials and seals and devices using such sealing materials | |
| RU2403136C2 (en) | Soldered system with matched thermal expansion factors (tef) | |
| CN100448066C (en) | A sealing material of solid oxide fuel cell and its sealing method | |
| WO2003092106A1 (en) | Multi-layer seal for electrochemical devices | |
| JP3495654B2 (en) | Cell tube seal structure | |
| CN108511641B (en) | Sealing gasket and composite glass sealing method for aluminum-shell power lithium ion battery | |
| CN1655386A (en) | Method for connecting ceramal in solid oxide fuel battery | |
| JP2014096277A (en) | Seal material for solid oxide type fuel battery use | |
| CN101075665A (en) | Solid oxide fuel cell sealing material bettween 500-800 deg.C intermediate temperature and its production | |
| JP2019515415A (en) | Solid oxide fuel cell | |
| CN1315223C (en) | High reliability long life solid oxide fuel battery and process for preparation | |
| CN105397336A (en) | Composite brazing filler material for sealing flat plate type solid oxide fuel battery and brazing method of composite brazing filler material | |
| CN1095598C (en) | High-temp. sealing material and sealing technology for soild oxide fuel cells | |
| KR101013845B1 (en) | Manufacturing Method of Sealing Glass for Intermediate Temperature Planar SOFC | |
| EP3890080A1 (en) | Sealant glass composition and solid oxide fuel cell using same | |
| JP2017534555A (en) | Method for forming a glass composition | |
| EP3875439A1 (en) | Sealing glass composition and solid oxide fuel cell using same | |
| CN109841868B (en) | Solid oxide fuel cell composite sealant and application thereof | |
| CN1884423B (en) | Complex phase seal material for solid oxide fuel cell and its preparation method | |
| Cela et al. | INFLUENCE OF FILLER ADDITIVES ON THE EFFECTIVE VISCOSITY OF GLASS-CERAMIC COMPOSITE SEALANTS. | |
| KR20220069213A (en) | Glass ceramic composite sealant for solid oxide fuel cell with low shrinkage | |
| KR101782609B1 (en) | Glass sealant for solid oxide fuel cell and sealing method using the same | |
| WO2023128812A1 (en) | Method for manufacturing tubular solid oxide fuel cells and battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |