CN100589271C - Preparation method of hollow fiber type solid oxide fuel cell - Google Patents
Preparation method of hollow fiber type solid oxide fuel cell Download PDFInfo
- Publication number
- CN100589271C CN100589271C CN200810024683A CN200810024683A CN100589271C CN 100589271 C CN100589271 C CN 100589271C CN 200810024683 A CN200810024683 A CN 200810024683A CN 200810024683 A CN200810024683 A CN 200810024683A CN 100589271 C CN100589271 C CN 100589271C
- Authority
- CN
- China
- Prior art keywords
- preparation
- electrolyte
- anode
- organic
- hollow fiber
- 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.)
- Expired - Fee Related
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000446 fuel Substances 0.000 title claims abstract description 24
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 23
- 239000007787 solid Substances 0.000 title claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 60
- 238000010438 heat treatment Methods 0.000 claims abstract description 48
- 239000000843 powder Substances 0.000 claims abstract description 23
- 238000005507 spraying Methods 0.000 claims abstract description 23
- 239000003960 organic solvent Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000000725 suspension Substances 0.000 claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 39
- 239000000758 substrate Substances 0.000 claims description 34
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000007921 spray Substances 0.000 claims description 15
- 239000010405 anode material Substances 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- -1 lanthanide metal oxide Chemical class 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002472 Starch Polymers 0.000 claims description 7
- 229910000510 noble metal Inorganic materials 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 235000019698 starch Nutrition 0.000 claims description 7
- 239000008107 starch Substances 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 239000001856 Ethyl cellulose Substances 0.000 claims description 4
- 229920002301 cellulose acetate Polymers 0.000 claims description 4
- 229920001249 ethyl cellulose Polymers 0.000 claims description 4
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 12
- 238000000498 ball milling Methods 0.000 description 10
- 239000002002 slurry Substances 0.000 description 9
- 239000012159 carrier gas Substances 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000012528 membrane Substances 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000006257 cathode slurry Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000004626 scanning electron microscopy Methods 0.000 description 6
- HBAGRTDVSXKKDO-UHFFFAOYSA-N dioxido(dioxo)manganese lanthanum(3+) Chemical compound [La+3].[La+3].[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O HBAGRTDVSXKKDO-UHFFFAOYSA-N 0.000 description 5
- 238000000713 high-energy ball milling Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000009849 vacuum degassing Methods 0.000 description 4
- 229910002127 La0.6Sr0.4Co0.2Fe0.8O3 Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000001218 confocal laser scanning microscopy Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910002738 Ba0.5Sr0.5Co0.8Fe0.2O3 Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910002147 La0.6Sr0.4FeO3 Inorganic materials 0.000 description 2
- 229910002148 La0.6Sr0.4MnO3 Inorganic materials 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 229910002204 La0.8Sr0.2MnO3 Inorganic materials 0.000 description 1
- 229910002806 Sm0.2Ce0.8O1.9 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- HHGOZPNFORUMTL-UHFFFAOYSA-N scandium strontium Chemical compound [Sc][Sr] HHGOZPNFORUMTL-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Images
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
Landscapes
- Fuel Cell (AREA)
- Inert Electrodes (AREA)
Abstract
The invention discloses a preparation method of a hollow fiber type solid oxide fuel cell, which comprises the following steps: adding the anode raw material into an organic solvent containing organic matters, uniformly mixing, forming to obtain an anode blank, and uniformly spraying an organic solvent suspension containing electrolyte powder onto the heat-treated anode blank to obtain an electrolyte layer; adding the cathode powder and the organic pore-forming agent into an organic solvent, uniformly dispersing to obtain an organic matter suspension containing the cathode powder, uniformly spraying the organic matter suspension onto an electrolyte layer, and performing heat treatment to obtain the hollow fiber type solid oxide fuel cell. The hollow fiber type SOFC structure is adopted, the diameter of the tubular SOFC is greatly reduced, and the power density of the SOFC in unit volume is improved by 3-10 times. Meanwhile, the reduction of the diameter also greatly reduces the thickness of the electrode and the electrolyte, so that the resistance on the electrode and the electrolyte is reduced, and the performance of the battery is improved. The invention can reduce the preparation cost and simplify the preparation process.
Description
Technical field
The invention belongs to novel energy, materials processing and power domain, be specifically related to a kind of hollow fiber type preparation of solid oxide fuel cell.
Background technology
Solid Oxide Fuel Cell (SOFC) is a kind of device that chemical energy is converted into electric energy.It is made of the electrolyte of one deck densification and the electrode of two-layer porous, and entire cell all adopts solid material, and this makes the life-span of battery can reach 40000~80000 hours.Different with the generation mode of routine, need not participate in by large-size machine during the SOFC generating, therefore whole process is very quiet, does not need to use lubricating oil that motor is safeguarded simultaneously, has reduced the use cost of SOFC.The working temperature of SOFC higher (500~1000 ℃), this makes the generating efficiency of SOFC can reach 40%~50%, if waste heat is used for thermo-mechanical power generation, the comprehensive utilization ratio of energy can reach more than 80%.Hot operation also makes SOFC so not harsh aspect the selection of fuel, and hydrogen, carbon monoxide, alcohols (methyl alcohol, ethanol) and alkane (methane, propane even isooctane) can both be as its fuel.Wherein, most of fuel is the recyclability resource, and this advantage makes SOFC become particularly important in today of energy shortage.And the use of non-fossil class A fuel A has reduced the generation of sulfur-containing oxide and nitrogen-containing oxide, and the efficient utilization of adding fuel can reduce emission of carbon-dioxide, and this makes SOFC become a kind of Blast Furnace Top Gas Recovery Turbine Unit (TRT) of very clean environment firendly again.
In actual applications, the power of monomer SOFC is very limited, in order to obtain bigger power, need with several monocells in every way (series, parallel, series-parallel connection) be assembled into battery pile (Stack).The SOFC of extensive generating piles up the battery pile that forms by single cell units by various structures, uses two kinds of maximum structures at present and is: flat and tube designs.Compare with flat-plate-type solid-oxide fuel battery, tubular solid oxide fuel cells (TSOFC) is more suitable in building big capacity power station because of characteristics such as the Sealing Technology of high mechanical properties, high thermal shock resistance, simplification, the integrated performances of high modularization.Because to prepare difficulty bigger for tubular cells, family surplus the unit that is engaged in the TSOFC research and development has only 30, and realize the above generate output of 100kW have only Siemens-Xi room power (SWPC) company.In addition, Acumentrics company and fuel cell technology company (Fuel Cell Technology FCT) has also obtained great advance in the exploitation of small-sized TSOFC.
But traditional tubular type SOFC generally needs the thicker supporter of one deck to guarantee the enough mechanical strengths of SOFC because the pipe diameter is bigger, generally adopts male or female support type SOFC, and this increases the resistance on the male or female, and the generating capacity of battery descends.And the response area that provides in traditional tubular type SOFC unit volume is still limited, so volumetric power density is still waiting to improve.
Summary of the invention
The object of the present invention is to provide a kind of high volumetric power density and be convenient to New type of S OFC configuration of production application and preparation method thereof.
Purpose of the present invention can reach by following measure:
A kind of hollow fiber type preparation of solid oxide fuel cell comprises the steps:
(1) anode material is added contain and mixes aftershaping in the organic organic solvent and make the anode base substrate, behind the dry solidification at 800~1200 ℃ of following heat treatment 3~96h;
(2) organic solvent suspension that will contain the electrolyte powder evenly sprays on the heat treated anode base substrate, heating anode base substrate to temperature is 80~250 ℃ during spraying, to spray electrolytical anode base substrate at 1200~1600 ℃ of following heat treatment 3~96h, make dielectric substrate;
(3) make the organic substance suspension that contains cathode powder with being uniformly dispersed in cathode powder and the organic pore-forming agents adding organic solvent, and evenly spray on the dielectric substrate, heating anode base substrate to temperature is 80~250 ℃ during spraying, spray the back at 800~1200 ℃ of following heat treatment 3~96h, made the hollow fiber type Solid Oxide Fuel Cell.
Wherein anode material is selected from one or more in transition metal oxide, lanthanide metal oxide or the perofskite type oxide, can also comprise that perhaps mass content is 10~60% electrolyte.Anode material can also comprise that mass content is 0.1~30% noble metal.
Wherein organic substance is polyvinyl alcohol, cellulose acetate, starch, polyvinyl butyral resin, polysulfones, polyether sulfone or polyester.Organic solvent is selected from methyl alcohol, ethanol, ethylene glycol, isopropyl alcohol, acetone, toluene, N, N-dimethyl acetyl ammonia or N, one or more in the N-dimethyl sulfoxide (DMSO).
Wherein cathode powder is selected from one or more in perofskite type oxide or the noble metal, as La
0.6Sr
0.4MnO
3(LSM64), La
0.6Sr
0.4FeO
3(LSF64), Ba
0.5Sr
0.5Co
0.8Fe
0.2O
3(BSCF), La
0.6Sr
0.4Co
0.2Fe
0.8O
3, La
0.8Sr
0.2MnO
3(LSM82), La
0.8Sr
0.2Sc
0.2Mn
0.8O
3(LSCM)), La
2NiO
4, PrBaCo
2O
5, Pt or Pd etc., perhaps above-mentioned substance and electrolytical combination.
Wherein electrolyte is the stable zirconia (as: Y of yttrium
0.18Zr
0.82O
1.91(YSZ)), the stable zirconia (as: Sc of scandium
0.2Zr
0.80O
1.9(ScSZ)), samarium doping of cerium oxide (as: Sm
0.10Ce
0.9O
1.95(SDC), Gd
0.20Ce
0.8O
1.9Or lanthanum gallium based perovskite type (as: La (GDC))
0.8Sr
0.2Ga
0.8Mg
0.2O
3(LSGM)) oxide electrolyte.Organic pore-forming agents is starch, glycerine, polyvinyl alcohol, ethyl cellulose or polyvinyl butyral resin.
Purpose of the present invention specifically can reach by following measure:
A kind of hollow fiber type SOFC, its concrete preparation process is:
(1) preparation of anode support
At first, organic substance is dissolved in the organic solvent in 20~120 ℃, makes organic solution after dissolving stirs;
The percentage by weight of described component is: organic substance: organic solvent=5~40%: 60~90%;
Described organic substance is preferably selected for use from polyvinyl alcohol, cellulose acetate, starch, polyvinyl butyral resin, polysulfones, polyether sulfone or polyester etc.;
Described solvent is preferably selected from methyl alcohol, ethanol, ethylene glycol, acetone, toluene, N, N-dimethyl acetyl ammonia or N, one or more in the N-dimethyl sulfoxide (DMSO);
Then, anode material is added in the above-mentioned organic solution, under 20~50 ℃, mix by ball milling;
Described anode material is: transition metal oxide (as: NiO, CuO, Fe
2O
3Deng), lanthanide metal oxide (as: La
2O
3, Sm
2O
3Deng) or perofskite type oxide (as: lanthanum manganate that chromium mixes, the lanthanum manganate that iron mixes, the lanthanum manganate that scandium mixes etc.); Described anode material can also be the mixture of above-mentioned substance and electrolyte (as: zirconia (YSZ) that yttrium is stable, the zirconia (ScSZ) that scandium is stable, samarium doping of cerium oxide (SDC), lanthanum gallium based perovskite type oxide (LSGM) electrolyte etc.); Mass ratio is an anode material: electrolyte=40~90%: 10~60%.
Described anode material can also add the composite material that noble metal (as Ag, Pt, Pd, Ru etc.) is formed for above-mentioned anode; The quality of noble metal accounts for 0.1~30% of anode.
Anode material and organic mass ratio are: 60~99%: 1~40%.
Then, with the above-mentioned organic solution that contains anode material, through passing through the extrusion molding of system film die after the vacuum degassing, make base substrate, dry solidification under room temperature or vacuum state promptly gets the anode base substrate; Again with the anode base substrate at 800~1200 ℃ of following heat treatment 3~96h;
Described system film die is special copper, the doughnut spinning head apparatus of aluminum or stainless steel;
The internal diameter of described anode base substrate is 0.4~2mm, and wall thickness is 0.2~0.8mm, and length is 5~150cm.
(2) electrolytical preparation
Dielectric substrate is by wet granular spray-on process (Wet Powder Spraying, WPS) preparation.The organic solvent suspension that will contain the electrolyte powder is passed through sprayer unit, be sprayed onto uniformly on the above-mentioned heat treated anode support, need heat the anode base substrate during spraying, temperature is 80~250 ℃, carrier gas can be any nonhazardous gas, carrier gas flux is 20~100mL/min, and gas pressure is 1~5atm, spray time 1~10s.The electrolyte of the anode-supported that above-mentioned spraying is finished places high-temperature electric resistance furnace to heat-treat, and makes the electrolyte densification, and sintering temperature is 1200~1600 ℃, and heating rate is 0.5~20 ℃/min, temperature retention time 3~96h.
The electrolyte powder adopts hydro thermal method synthetic, and the electrolyte particle diameter is 50~400nm;
The electrolyte powder is placed organic solvent, mix 30~240min by high-energy ball milling machinery and make it even;
Organic solvent is preferably selected for use in ethylene glycol, isopropyl alcohol, acetone, ethanol or methyl alcohol etc.;
The mass ratio of electrolyte powder and organic solvent is 0.5~30: 100;
(3) preparation of negative electrode
Cathode powder and organic pore-forming agents added in the organic solvent to be uniformly dispersed through high-energy ball milling make the organic substance suspension that contains cathode powder, utilize the above-mentioned spraying method identical that negative electrode suspension is sprayed onto fine and close bath surface with electrolyte, need heat the anode base substrate during spraying, temperature is 80~250 ℃, heat treatment makes required battery in electric furnace again, sintering temperature is 800~1200 ℃, and heating rate is 0.5~20 ℃/min, temperature retention time 3~96h.Final battery interior diameter only is 0.3~1.5mm, wall thickness 0.15~0.60mm, length be 3~120cm (after high-temperature heat treatment, sintering can take place in ceramic material, shrinkage about 30% or more than, so size is inconsistent before and after can causing sintering).
Cathode material is the various perofskite type oxides (as: lanthanum manganate (as: La of strontium doping
0.8Sr
0.2MnO
3(LSM82)), the lanthanum manganate (as: La of strontium scandium doping
0.8Sr
0.2Sc
0.2Mn
0.8O
3(LSCM)), noble metal (as: Pt, Pd etc.) or other perovskite-like type oxide (as: La
2NiO
4, PrBaCo
2O
5Deng); Cathode material also can be the mixture that above two or more material is formed arbitrarily, with and the mixture (as: Ba that forms arbitrarily with electrolyte
0.5Sr
0.5Co
0.8Fe
0.2O
3(BSCF)+and Ag, LSM+YSZ, LSCM+ScSZ+Pd, BSCF+SDC+Ag etc.).
Organic pore-forming agents is preferably selected for use in starch, glycerine, polyvinyl alcohol, polyvinyl butyral resin, ethyl cellulose or various material with carbon elements etc.; Organic solvent is preferably selected for use in ethylene glycol, isopropyl alcohol, acetone, ethanol or methyl alcohol etc.; The mass ratio of organic pore-forming agents and organic solvent is 5~30: 60~120, and the mass ratio of cathode material and organic solvent is 5~20: 90~120.
The thickness of the negative electrode after the heat treatment is 5~200 μ m.
Beneficial effect of the present invention:
The present invention adopts hollow fiber type SOFC structure, has dwindled the diameter of tubular type SOFC greatly, makes the power density of SOFC in unit volume improve 3~10 times.Dwindling of diameter also makes electrode and electrolytical thickness significantly reduce simultaneously, so the resistance on electrode and the electrolyte descends the raising battery performance thereupon.In addition, the present invention adopts the WPS technology to prepare the preparation cost that electrolyte and negative electrode can reduce SOFC, simplifies the preparation technology of SOFC.
Description of drawings
Fig. 1 is scanning electron microscopy (SEM) photo of bath surface behind the embodiment of the invention one sintering.
Fig. 2 is a negative electrode behind the embodiment of the invention one sintering | electrolyte | and the SEM photo in anode trilamellar membrane cross section.
Fig. 3 is current density-voltage (I-V) and current density-power density (I-W) curve of the embodiment of the invention one hollow fiber type SOFC.
Fig. 4 is a negative electrode behind the embodiment of the invention two sintering | electrolyte | and the SEM photo in anode trilamellar membrane cross section.
Fig. 5 is I-V and the I-W curve of the embodiment of the invention two hollow fiber type SOFC.
Embodiment
Embodiment 1:Ni+Y
0.18Zr
0.82O
1.91(YSZ) | YSZ|La
0.6Sr
0.4MnO
3(LSM64) preparation of hollow fiber type SOFC and performance test
At first, with the 5g polyvinyl butyral resin, 40g ethanol, 10g acetone, 10g N, the premixed of N-dimethyl acetyl ammonia takes by weighing 40gNiO and 60gYSZ powder more respectively and adds in the stainless steel jar mill, forms organic substance-metal oxide paste behind the ball milling 24h.To make the anode base substrate some with extruding by the system film die after the above-mentioned slurry vacuum degassing, with this base substrate under the vacuum state in 80 ℃ of dry 24h be placed in the electric furnace 1000 ℃ of heat treatment 5h (heating rate be 5 ℃/after min) dry body body (internal diameter 1.5mm, thickness 0.8mm, long 200mm).
Then, with electrolyte powder 10g YSZ, 20g ethylene glycol, the 80g isopropyl alcohol adds in the ball grinder, and ball milling 2h makes electrolyte slurry under the 500rpm rotating speed.By the excusing from death sprayer inferior electrolyte slurry is sprayed on the above-mentioned anode dry body body, anode dry body body must be placed on the heating station in spraying process, and temperature is 200 ℃, and carrier gas is an argon gas, and flow is 50mL/min, and gas pressure is 1.2atm, spray time 4s.The double-deck base substrate of the electrolyte of the anode-supported that above-mentioned spraying is finished places high-temperature electric resistance furnace heat treatment, and treatment temperature is 1400 ℃, and heating rate is 3 ℃/min, temperature retention time 5h.After finishing, heat treatment obtains the electrolyte duplicature of anode-supported.Fig. 1 can see from photo that for electrolytical scanning electron microscopy (SEM) photo after the heat treatment whole bath surface is fine and close fully, exists without any hole or crack.
Secondly, by high-energy ball milling with 5g LSM64,10g ethylene glycol, 40g isopropyl alcohol and 5g polyvinyl alcohol (organic pore-forming agents) add in the ball grinder, ball milling 2h makes cathode slurry under the 500rpm rotating speed.The secondary cathode slurry is sprayed on the dielectric substrate of electrolyte duplicature of above-mentioned anode-supported by the excusing from death sprayer, anode dry body body must be placed on the heating station in spraying process, and temperature is 200 ℃, carrier gas is an argon gas, flow is 50mL/min, and gas pressure is 1.2atm, spray time 6s.The negative electrode that spraying is good | electrolyte | the anode trilamellar membrane places high-temperature electric resistance furnace heat treatment, and treatment temperature is 1050 ℃, and heating rate is 5 ℃/min, temperature retention time 5h.Get hollow fiber type SOFC after the heat treatment.Fig. 2 is a negative electrode | electrolyte | and the SEM photo in anode trilamellar membrane cross section, electrolyte are approximately 10 μ m, almost do not have the hole, and density is very high, so ionic conducting property is good.The negative electrode anode is loose structure, and they are connected very closely with electrolytical, help the conduction of oxonium ion in negative electrode-electrolyte or electrolyte-anodic interface.
At last, carry out the test of hollow fiber type fuel battery performance.Interior pipe feeds hydrogen and acts as a fuel, and the outer tube bubbling air is as oxidant.As can be seen from Figure 3, open circuit voltage is that 1.03V this and theoretical value are very approaching in the time of 850 ℃, illustrates that there is not flaw in electrolyte, and power density can reach 917mW/cm
2
Embodiment 2:Ni+Sc
0.2Zr
0.80O
1.9(ScSZ) | ScSZ|La
0.6Sr
0.4FeO
3(LSF64) preparation of hollow fiber type SOFC and performance test
At first, with the 5g polyvinyl butyral resin, 40g ethylene glycol, the 10g butanone, 20g N, the premixed of N-dimethyl sulfoxide (DMSO) takes by weighing 40gNiO and 60g ScSZ powder more respectively and adds in the stainless steel jar mill, forms organic substance-metal oxide paste behind the ball milling 48h.Some with going out to make the anode base substrate by system film die skill after the above-mentioned slurry vacuum degassing, with this base substrate under the vacuum state in 100 ℃ of dry 24h be placed in the electric furnace 1000 ℃ of heat treatment 5h (heating rate be 5 ℃/after min) dry body body (internal diameter 1mm, thickness 0.6mm, long 150mm).
Then, with electrolyte powder 10g ScSZ, 10g ethylene glycol, 10g toluene, the 80g isopropyl alcohol adds in the ball grinder, and ball milling 2h makes electrolyte slurry under the 500rpm rotating speed.By the excusing from death sprayer inferior electrolyte slurry is sprayed on the above-mentioned anode dry body body, anode dry body body must be placed on the heating station in spraying process, and temperature is 200 ℃, and carrier gas is an argon gas, and flow is 50mL/min, and gas pressure is 1.5atm, spray time 8s.The double-deck base substrate of the electrolyte of the anode-supported that above-mentioned spraying is finished places high-temperature electric resistance furnace heat treatment, and treatment temperature is 1400 ℃, and heating rate is 4 ℃/min, temperature retention time 5h.After finishing, heat treatment obtains the electrolyte duplicature of anode-supported.
Secondly, by high-energy ball milling with 5g LSF64,10g ethylene glycol, 40g isopropyl alcohol and 10g starch (organic pore-forming agents) add in the ball grinder, ball milling 2h makes cathode slurry under the 500rpm rotating speed.The secondary cathode slurry is sprayed on the dielectric substrate of electrolyte duplicature of above-mentioned anode-supported by the excusing from death sprayer, anode dry body body must be placed on the heating station in spraying process, and temperature is 250 ℃, carrier gas is a nitrogen, flow is 30mL/min, and gas pressure is 1.0atm, spray time 10s.The negative electrode that spraying is good | electrolyte | the anode trilamellar membrane places high-temperature electric resistance furnace heat treatment, and treatment temperature is 1000 ℃, and heating rate is 5 ℃/min, temperature retention time 3h.Get hollow fiber type SOFC after the heat treatment.Fig. 4 is a negative electrode | electrolyte | and the SEM photo in anode trilamellar membrane cross section, electrolyte are approximately 16 μ m, almost do not have the hole, and density is very high, so ionic conducting property is good.The negative electrode anode is loose structure, and they are connected very closely with electrolytical, help the conduction of oxonium ion in negative electrode-electrolyte or electrolyte-anodic interface.
At last, carry out the test of hollow fiber type fuel battery performance.Interior pipe feeds hydrogen and acts as a fuel, and the outer tube bubbling air is as oxidant.As can be seen from Figure 5, open circuit voltage is that 1.06V this and theoretical value are very approaching in the time of 850 ℃, illustrates that there is not flaw in electrolyte, and power density can reach 600mW/cm
2
Embodiment 3:Ni+Sm
0.2Ce
0.8O
1.9(SDC) | preparation and the performance test of SDC|BSCF+SDC hollow fiber type SOFC
At first, with the 5g polyvinyl butyral resin, 40g ethylene glycol, the 10g butanone, 20g N, the premixed of N-dimethyl sulfoxide (DMSO) takes by weighing 40gNiO and 60g SDC powder more respectively and adds in the stainless steel jar mill, forms organic substance-metal oxide paste behind the ball milling 48h.Some with going out to make the anode base substrate by system film die skill after the above-mentioned slurry vacuum degassing, with this base substrate under the vacuum state in 100 ℃ of dry 24h be placed in the electric furnace 1000 ℃ of heat treatment 5h (heating rate be 5 ℃/after min) dry body body (internal diameter 1mm, thickness 0.6mm, long 150mm).
Then, with electrolyte powder 10g ScSZ, 10g ethylene glycol, 10g toluene, the 80g isopropyl alcohol adds in the ball grinder, and ball milling 2h makes electrolyte slurry under the 500rpm rotating speed.By the excusing from death sprayer inferior electrolyte slurry is sprayed on the above-mentioned anode dry body body, anode dry body body must be placed on the heating station in spraying process, and temperature is 200 ℃, and carrier gas is a nitrogen, and flow is 50mL/min, and gas pressure is 1.5atm, spray time 6s.The double-deck base substrate of the electrolyte of the anode-supported that above-mentioned spraying is finished places high-temperature electric resistance furnace heat treatment, and treatment temperature is 1400 ℃, and heating rate is 4 ℃/min, temperature retention time 5h.After finishing, heat treatment obtains the electrolyte duplicature of anode-supported.
Secondly, by high-energy ball milling with 1.5g BSCF, 3.5gSDC, 10g ethylene glycol, 40g isopropyl alcohol and 8g ethyl cellulose (organic pore-forming agents) add in the ball grinder, ball milling 4h makes cathode slurry under the 450rpm rotating speed.The secondary cathode slurry is sprayed on the dielectric substrate of electrolyte duplicature of above-mentioned anode-supported by the excusing from death sprayer, anode dry body body must be placed on the heating station in spraying process, and temperature is 250 ℃, carrier gas is a nitrogen, flow is 30mL/min, and gas pressure is 1.0atm, spray time 6s.The negative electrode that spraying is good | electrolyte | the anode trilamellar membrane places high-temperature electric resistance furnace heat treatment, and treatment temperature is 950 ℃, and heating rate is 10 ℃/min, temperature retention time 10h.Get hollow fiber type SOFC after the heat treatment.
Embodiment 4: organic matter removal replaces with cellulose acetate, and electrolyte replaces with La
0.8Sr
0.2Ga
0.8Mg
0.2O
3, anode material replaces with CuO, and negative electrode replaces with Ba
0.5Sr
0.5Co
0.8Fe
0.2O
3(BSCF)+Ag outside, other are with embodiment 1.
Embodiment 5: remove anode and replace with Cu+GDC+Sm
2O
3, negative electrode replaces with La
0.6Sr
0.4Co
0.2Fe
0.8O
3Outward, other are with embodiment 2.
Embodiment 6: remove anode and replace with Cu+La
0.8Sr
0.2Ga
0.8Mg
0.2O
3+ Pt, negative electrode replaces with La
0.6Sr
0.4Co
0.2Fe
0.8O
3Outside+the SDC+Ag, other are with embodiment 3.
Claims (10)
1, a kind of hollow fiber type preparation of solid oxide fuel cell is characterized in that comprising the steps:
(1) anode material is added contain and mixes aftershaping in the organic organic solvent and make the anode base substrate, behind the dry solidification at 800~1200 ℃ of following heat treatment 3~96h;
(2) organic solvent suspension that will contain the electrolyte powder evenly sprays on the heat treated anode base substrate, heating anode base substrate to temperature is 80~250 ℃ during spraying, to spray electrolytical anode base substrate at 1200~1600 ℃ of following heat treatment 3~96h, make dielectric substrate;
(3) make the organic substance suspension that contains cathode powder with being uniformly dispersed in cathode powder and the organic pore-forming agents adding organic solvent, and evenly spray on the dielectric substrate, heating anode base substrate to temperature is 80~250 ℃ during spraying, spray the back at 800~1200 ℃ of following heat treatment 3~96h, made the hollow fiber type Solid Oxide Fuel Cell.
2, preparation method according to claim 1 is characterized in that described anode material is selected from one or more in transition metal oxide or the lanthanide metal oxide, comprises also that perhaps mass content is 10~60% electrolyte.
3, preparation method according to claim 1 is characterized in that described anode material comprises that also mass content is 0.1~30% noble metal.
4, preparation method according to claim 1, the internal diameter that it is characterized in that described anode base substrate is 0.4~2mm, and wall thickness is 0.2~0.8mm, and length is 5~150cm.
5, preparation method according to claim 1 is characterized in that the organic substance described in the step (1) is polyvinyl alcohol, cellulose acetate, starch, polyvinyl butyral resin, polysulfones, polyether sulfone or polyester.
6, preparation method according to claim 1 is characterized in that described organic solvent is selected from methyl alcohol, ethanol, ethylene glycol, isopropyl alcohol, acetone, butanone, toluene, N, N-dimethyl acetyl ammonia or N, one or more in the N-dimethyl sulfoxide (DMSO).
7, preparation method according to claim 1 is characterized in that described cathode powder is selected from one or more in perofskite type oxide or the noble metal, perhaps above-mentioned substance and electrolytical combination.
8 according to claim 1,3 or 7 described preparation methods, it is characterized in that described electrolyte is the stable zirconia of the stable zirconia of yttrium, scandium, samarium doping of cerium oxide or lanthanum gallium based perovskite type oxide electrolyte.
9 preparation methods according to claim 1 is characterized in that described organic pore-forming agents is starch, glycerine, polyvinyl alcohol, ethyl cellulose or polyvinyl butyral resin.
10, preparation method according to claim 1, the interior diameter that it is characterized in that described hollow fiber type Solid Oxide Fuel Cell is 0.3~1.5mm, wall thickness 0.15~0.60mm, length is 3~120cm.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN200810024683A CN100589271C (en) | 2008-04-01 | 2008-04-01 | Preparation method of hollow fiber type solid oxide fuel cell |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN200810024683A CN100589271C (en) | 2008-04-01 | 2008-04-01 | Preparation method of hollow fiber type solid oxide fuel cell |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101252199A CN101252199A (en) | 2008-08-27 |
CN100589271C true CN100589271C (en) | 2010-02-10 |
Family
ID=39955460
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN200810024683A Expired - Fee Related CN100589271C (en) | 2008-04-01 | 2008-04-01 | Preparation method of hollow fiber type solid oxide fuel cell |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN100589271C (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101752585B (en) * | 2010-01-21 | 2011-11-16 | 南京工业大学 | Solid oxide fuel cell system and preparation method thereof |
CN101775610B (en) * | 2010-03-05 | 2012-09-19 | 南京工业大学 | Solid electrochemical oxygen pump and carbon dioxide decomposition method thereof |
CN102347495B (en) * | 2011-10-19 | 2014-01-08 | 华北电力大学 | Solid oxide fuel cell structure and preparation method thereof |
CN103103556B (en) * | 2013-03-06 | 2015-05-20 | 景德镇陶瓷学院 | Tubular ceramic membrane reactor and methanol synthesis method implemented by using same |
CN103613067B (en) * | 2013-11-22 | 2015-10-28 | 山东理工大学 | The method of synthetic gas is prepared in humidify carbon dioxide electrocatalysis |
CN104577142B (en) * | 2014-12-18 | 2017-07-07 | 天津工业大学 | A kind of preparation method of SOFC gradient-structure cathodic coating |
CN104638287A (en) * | 2015-01-28 | 2015-05-20 | 潮州三环(集团)股份有限公司 | Method for preparing anode-supported type solid oxide fuel battery |
CN106601986A (en) * | 2016-12-29 | 2017-04-26 | 中国电子科技集团公司第十八研究所 | Preparation method of AGO electrode |
CN108039506B (en) * | 2017-12-07 | 2020-05-19 | 山东理工大学 | Preparation method of hollow fiber solid oxide fuel cell with petal-shaped cross section |
CN111244467B (en) * | 2018-11-27 | 2021-08-03 | 中国科学院大连化学物理研究所 | Method for stabilizing cathode of solid oxide fuel cell |
-
2008
- 2008-04-01 CN CN200810024683A patent/CN100589271C/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CN101252199A (en) | 2008-08-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN100589271C (en) | Preparation method of hollow fiber type solid oxide fuel cell | |
CN102290589B (en) | Cathode-supported direct carbon fuel cell | |
CN109904497B (en) | Anti-carbon-deposition metal-supported solid oxide fuel cell and preparation method thereof | |
CN101577340B (en) | Method for preparing cathode-supported tubular solid oxide fuel cells | |
CN101359746B (en) | Large size tubular solid oxide fuel cell and preparation thereof | |
KR100648144B1 (en) | High performance anode-supported solide oxide fuel cell | |
Xie et al. | Electrochemical gas–electricity cogeneration through direct carbon solid oxide fuel cells | |
CN101399352B (en) | Producing method for a high strength ultra-thin anode supporting type solid oxide fuel cell | |
CN100399611C (en) | Method for preparing solid oxide fuel cell cathode load type half-cell | |
CN102903945B (en) | Method for preparing large-size flat plate type metal supporting solid oxide fuel cell | |
CN101540411A (en) | Solid electrolyte direct carbon fuel cell | |
CN104332635B (en) | A kind of SOFC and preparation method thereof | |
CN102903940B (en) | Asymmetric composite anode of microtuble-type solid oxide fuel cell and preparation method of asymmetric composite anode | |
US9627703B2 (en) | Medium and high-temperature carbon-air cell | |
CN107785598B (en) | Half-cell symmetrical solid oxide fuel cell | |
CN101577341A (en) | Method for preparing solid oxide fuel cell and entire cell thereof at low temperature | |
CN102881930A (en) | Method for preparing flat-plate type metal-support solid oxide fuel cell | |
CN107017423B (en) | Low-temperature solid oxide fuel cell and preparation method thereof | |
CN113337834B (en) | Asymmetric-structure electrolytic cell made of symmetric materials and preparation method thereof | |
KR20130047534A (en) | Solid oxide fuel cell and solid oxide electrolysis cell including ni-ysz fuel(hydrogen) electrode, and fabrication method thereof | |
CN111029592B (en) | Honeycomb high-performance solid oxide reversible battery hydrogen electrode material and preparation method thereof | |
Sun et al. | Evaluation of Sr0. 88Y0. 08TiO3–CeO2 as composite anode for solid oxide fuel cells running on CH4 fuel | |
CN103840185A (en) | Solid oxide fuel cell containing quasi-symmetric composite membrane electrode and preparation method thereof | |
CN101752585B (en) | Solid oxide fuel cell system and preparation method thereof | |
CN114094123A (en) | Anode/electrolyte half cell, anode-supported solid oxide fuel cell and method for manufacturing the same |
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 | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100210 Termination date: 20140401 |