CN100595952C - High-temperature fuel cell system having anode loading functional coating with methane as main fuel - Google Patents
High-temperature fuel cell system having anode loading functional coating with methane as main fuel Download PDFInfo
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- CN100595952C CN100595952C CN200810124397A CN200810124397A CN100595952C CN 100595952 C CN100595952 C CN 100595952C CN 200810124397 A CN200810124397 A CN 200810124397A CN 200810124397 A CN200810124397 A CN 200810124397A CN 100595952 C CN100595952 C CN 100595952C
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000000446 fuel Substances 0.000 title claims abstract description 91
- 238000000576 coating method Methods 0.000 title claims abstract description 24
- 239000011248 coating agent Substances 0.000 title claims abstract description 15
- 238000011068 loading method Methods 0.000 title claims description 4
- 239000007787 solid Substances 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 238000006057 reforming reaction Methods 0.000 claims abstract description 8
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 45
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 16
- 239000004471 Glycine Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- 238000002485 combustion reaction Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 230000002269 spontaneous effect Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- KMRWEOROUHYRCC-UHFFFAOYSA-N [Mn].[Sc].[Sr].[La] Chemical compound [Mn].[Sc].[Sr].[La] KMRWEOROUHYRCC-UHFFFAOYSA-N 0.000 claims description 4
- PACGUUNWTMTWCF-UHFFFAOYSA-N [Sr].[La] Chemical compound [Sr].[La] PACGUUNWTMTWCF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- RIVZIMVWRDTIOQ-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co].[Co] RIVZIMVWRDTIOQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- CEUHVTHXJSTYJV-UHFFFAOYSA-N [Co].[Sc].[Sr] Chemical compound [Co].[Sc].[Sr] CEUHVTHXJSTYJV-UHFFFAOYSA-N 0.000 claims description 2
- QBYHSJRFOXINMH-UHFFFAOYSA-N [Co].[Sr].[La] Chemical compound [Co].[Sr].[La] QBYHSJRFOXINMH-UHFFFAOYSA-N 0.000 claims description 2
- XIPYTWGOABLHAF-UHFFFAOYSA-N [Mn].[Cr].[Sr].[La] Chemical compound [Mn].[Cr].[Sr].[La] XIPYTWGOABLHAF-UHFFFAOYSA-N 0.000 claims description 2
- XGPJPLXOIJRLJN-UHFFFAOYSA-N [Mn].[Sr].[La] Chemical compound [Mn].[Sr].[La] XGPJPLXOIJRLJN-UHFFFAOYSA-N 0.000 claims description 2
- WOIHABYNKOEWFG-UHFFFAOYSA-N [Sr].[Ba] Chemical compound [Sr].[Ba] WOIHABYNKOEWFG-UHFFFAOYSA-N 0.000 claims description 2
- MUKNRCIFSDRESU-UHFFFAOYSA-N [Zr].[Sc] Chemical compound [Zr].[Sc] MUKNRCIFSDRESU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001938 gadolinium oxide Inorganic materials 0.000 claims description 2
- 229940075613 gadolinium oxide Drugs 0.000 claims description 2
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 2
- FWLGASJILZBATH-UHFFFAOYSA-N gallium magnesium Chemical compound [Mg].[Ga] FWLGASJILZBATH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910001954 samarium oxide Inorganic materials 0.000 claims description 2
- 229940075630 samarium oxide Drugs 0.000 claims description 2
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001960 metal nitrate Inorganic materials 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 3
- 229910052593 corundum Inorganic materials 0.000 abstract 3
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract 1
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 239000003345 natural gas Substances 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 239000000523 sample Substances 0.000 description 7
- 238000013112 stability test Methods 0.000 description 6
- 229910003310 Ni-Al Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 238000000713 high-energy ball milling Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FNYZJPWUOBLZSX-UHFFFAOYSA-N 2-aminoacetic acid;nitrous acid Chemical compound ON=O.NCC(O)=O FNYZJPWUOBLZSX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000007306 turnover Effects 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
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- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
The invention relates to solid oxide fuel cell technical field, in particular to a high temperature cell system which is loaded with a functional coating at the anode and takes firedamp as main fuel.A catalyzing coating is arranged on the surface of the anode of the cell; when firedamp is taken as the main fuel, carbon monoxide and inflammable air will be generated according to the partial oxidation of the firedamp and the reforming reaction inside the cell, and anti-carbon property of the anode will improved; the catalyzer of the catalyzing coating is NiO-Al2O3, or RuO2-Al2O3, or RuO2-CeO2,or NiO-Al2O3 with the additive of La2O3 and/or Li2O. The cell system partially oxidates the firedamp and combines good catalyzer in the reforming reaction with solid oxide fuel cell, thus improving the property of the firedamp fuel cell. The invention remarkably improves the power density and operational stability of the fuel cell and anti-carbon resistance of the anode; therefore the cell systemis applicable to portable fuel cell devices. Meanwhile, the exhaust gas can be recycled, thus minimizing influence to the environment.
Description
Technical field
The present invention relates to a kind of fuel cell system, relating in particular to a kind of is the high-temperature fuel cell system of fuel with methane at anode surface load one layer function catalyst coatings.
Background technology
Directly (be mainly CH with natural gas
4) be that the SOFC of fuel is the simplest on operation and equipment, begun to cause the great interest of people in the world, this begins to occur a large amount of articles about in this respect and can be verified from present open source literature.But there is methane electro-chemical activity low (particularly at low temperatures) in it, and the carbon distribution phenomenon easily takes place and causes shortcoming such as rapid deactivation in electrode surface, though directly methane SOFC aspect has demonstrated outstanding anti-carbon performance at present, but exist the lower electronic conductivity of perovskite anode and with the shortcomings such as adhesive capacity of traditional electrolyte difference, so direct in the world at present methane (natural gas) Solid Oxide Fuel Cell also is in the laboratory research stage, current research emphasis mainly concentrates on power density and the anti-carbon performance that how to improve direct methane fuel battery.Mainly concentrate on university research at present, U.S. University of Pennsyvalnia, Northwestern University and Britain University of St Andrews university are rather outstanding at this area research.
Solid Oxide Fuel Cell (SOFC) can be a fuel with hydrocarbon or its reformation gas directly as a kind of high-temperature fuel cell, have outstanding features such as high energy efficiency and low pollution, also has the big advantage of fuel selectable range that low-temperature fuel cell does not possess simultaneously: except pure hydrogen, CO, alcohol, hydrocarbon, coal gas, even ammonia can be as its fuel, it should be noted that simultaneously SOFC has higher power density, avoided low-temperature fuel cell can only use the shortcoming of noble metal electrode material simultaneously, SOFC is at stationary electric power plant, portable power source, the fields such as transportation and military affairs of moving all have a wide range of applications.Its successful Application and alleviation China energy crisis satisfy the requirement of people to the continuous lifting of amount of energy and quality, and the energy security of the living environment that protection is human and guarantee China is significant.In addition, the composition material of SOFC mostly is rare earth oxide, and China is rare earth reserves big countries, thereby exploitation SOFC also is significant for the rare earth resources that rationally utilizes China's abundant.Natural gas is a kind of important energy carrier, is that the fuel cell technology of fuel is significant for more rationally utilizing limited natural gas resource with the natural gas.Adopt high temperature SOFC, natural gas is catalytic oxidation on anode directly, makes fuel cell system configuration simplify greatly.Consider the electro catalytic activity that methane is lower, can adopt the interior reformation technology of fuel cell.
Summary of the invention
The objective of the invention is in order to solve the power density that how to improve direct methane fuel battery and the problem of anti-carbon performance, is the high-temperature fuel cell system of fuel thereby provide a kind of with methane at anode surface load one layer function catalyst coatings.
Technical scheme of the present invention is: a kind of anode loading functional coating be the solid oxide fuel battery system of main fuel with methane, it is characterized in that anode outer surface load one deck catalyst coatings at battery, when being main fuel with methane, partial oxidation and interior reforming reaction according to methane produce carbon monoxide and hydrogen, and increase the anti-carbon performance of anode; The catalyst of wherein said catalyst coatings is NiO-Al
2O
3, RuO
2-Al
2O
3Or RuO
2-CeO
2In a kind of, or at NiO-Al
2O
3In added La
2O
3And/or Li
2O.
Above-mentioned catalyst coatings has high catalytic activity to natural gas (methane) partial oxidation and reforming reaction.
When described anode-catalyzed coated catalysts is NiO-Al
2O
3, RuO
2-Al
2O
3, RuO
2-CeO
2In a kind of the time, the content of metal Ni or Ru is that the percentage by weight that accounts for the catalyst total amount is 5%-10% in the catalyst; When described anode-catalyzed coated catalysts is NiO-Al
2O
3In added La
2O
3And/or Li
2During O, the content of metal Ni is that the percentage by weight that accounts for the catalyst total amount is 5%-10% in the catalyst, La
2O
3And Li
2The content of O is the percentage by weight 3-10% that accounts for the catalyst total amount.
Battery of the present invention adopts tubular type or planar cells configuration.Battery configuration can adopt anode support type or electrolyte-supporting type.
Designed Solid Oxide Fuel Cell can adopt tubular type or flat design among the present invention, the electrolyte of battery adopts a kind of in samarium oxide doping of cerium oxide (SDC), gadolinium oxide doping of cerium oxide (GDC), yttrium stable zirconia (YSZ), lanthanum strontium gallium magnesium (LSGM) or the scandium zirconium (ScSZ), cathode material to adopt a kind of in Ca-Ti ore type lanthanum strontium manganese (LSM), lanthanum strontium scandium manganese (LSSM), barium strontium ferro-cobalt (BSCF), lanthanum strontium ferro-cobalt (LSCF), lanthanum strontium cobalt (LSC) or the strontium scandium cobalt (SSC); Anode adopts electrolyte/nickel composite anode, lanthanum strontium scandium manganese (LSSM) or lanthanum strontium chromium manganese (LSCM) Ca-Ti ore type anode.
The operating temperature of fuel cell system of the present invention is 600-1000 ℃.
The preparation method of anode coated catalysts is GNP (glycine nitrite process) method in the battery system, concrete steps are: the nitrate that takes by weighing various metals by stoichiometric proportion, use deionized water dissolving, add glycine, after treating to dissolve fully, this solution is heated to 80-120 ℃ of one-tenth under stirring condition thick, spontaneous combustion in baking oven then, and temperature is 200-300 ℃; 800-1000 ℃ of calcining 5-10 hour in Muffle furnace of cooling back; Grind into powder promptly makes desired catalyst.
The addition of above-mentioned glycine is the mol ratio (G/M of metal ion total in glycine and the nitrate
N+) than being 2: 1-3: 1.
The prepared catalyst of the present invention, such as Ni-Al
2O
3The catalyst partial oxidation reaction of methane is at CH at each temperature
4Conversion ratio and CO selectivity are better, catalytic methane steam, and CO 2 reforming reaction is at CH at each temperature
4Conversion ratio and CO selectivity are better, as Fig. 8 and shown in Figure 9.
Battery preparation method often can adopt at present the curtain coating of employing, spraying in conjunction with sintering method.Its structure as shown in figure 11.
The catalysis layer adopts " wet chemical method " preparation, preferred 1g catalyst powder adds the 10-20ml isopropyl alcohol, 0.6-1.2ml glycerine, 2-4ml ethylene glycol, take out after advancing high-energy ball milling 30-60min, adopt fully-automatic ultrasonic sprayed on membrane method accurately to prepare gas renormalizing catalysis layer, guarantee and the good adhesive strength of anode layer.The thickness of anode-catalyzed coating is 10 μ m-20 μ m..Its structure as shown in figure 12.
The fuel of fuel cell is the O of a methane and a part
2, H
2O, CO
2The act as a fuel fuel of battery, battery operation system (as shown in figure 10) is by the Solid Oxide Fuel Cell sheet, and turnover feed channel and heating furnace are formed, and fuel gas is supplied to battery sheet anode through interior pipe, and tail gas (is mainly CO
2And unreacted CH
4) discharge battery output current supply external circuit by outer tube.
Beneficial effect:
The present invention adopts the new function catalyst coatings (Ni-Al that gas by partial oxidation of natural and reforming reaction is had high catalytic activity at anode outer surface load last layer
2O
3, Ru-Al
2O
3, Ru-CeO
2And interpolation La
2O
3And/or Li
2The Ni-Al of O
2O
3In a kind of), fuel cell performance is greatly improved, as with methane, when oxygen was fuel, the power density of battery had increased by one times in the time of 850 ℃, had increased by three times in the time of 750 ℃.Significantly improved the anti-carbon performance of anode simultaneously.The objective of the invention is to natural gas is the exploitation of the middle temperature SOFC new material of fuel, many-sided researchs such as the design of battery configuration, form Solid Oxide Fuel Cell and be reformation technology in the self-heating of fuel with the natural gas, thereby realize with the natural gas being the high power density of fuel and the new system of Solid Oxide Fuel Cell of high stability, promote the development and the application of China SOFC technology, the reasonable utilization that improves China's natural gas and rare earth resources simultaneously.
Description of drawings
Fig. 1 is current density-voltage (I-V) and current density-power density (I-W) curve of battery in the embodiment of the invention 1.
Fig. 2 is the I-V and the I-W curve of the embodiment of the invention 2 batteries.
Fig. 3 is the I-V and the I-W curve of the embodiment of the invention 3 batteries.
Fig. 4 is the I-V and the I-W curve of the embodiment of the invention 4 batteries.
Fig. 5 is the I-V and the I-W curve of the embodiment of the invention 5 batteries.
Fig. 6 is the I-V and the I-W curve of the embodiment of the invention 6 batteries.
Fig. 7 is the I-V and the I-W curve of the embodiment of the invention 7 batteries.
Fig. 8 is Ni-Al
2O
3The CH at each temperature of catalyst partial oxidation reaction of methane
4Conversion ratio and CO selectivity curve.
Fig. 9 is Ni-Al
2O
3The catalyst methane vapor, the CH at each temperature of CO 2 reforming reaction
4Conversion ratio and CO selectivity curve.
Figure 10 is a fuel cell system device schematic diagram, and wherein 1 is the Solid Oxide Fuel Cell sheet, and 2 for the interior effective outlet pipe of doing, and 3 are used as CH for the outer tube air flue
4Air inlet, 4, quartz ampoule, 5, connect the hermetic collar assembly, A is an external circuit, and B is an air supply plant, and C is a gas vent.
Figure 11 is the detail drawing of Solid Oxide Fuel Cell sheet, and wherein 1-1 is a cell cathode, and 1-2 is a dielectric substrate, and 1-3 is a galvanic anode.
Figure 12 is the detail drawing of the Solid Oxide Fuel Cell sheet of interpolation catalyst coatings, and wherein 1-4 is anode-catalyzed coating.
Embodiment
Embodiment 1: with methane, oxygen is the Ni+ScSZ|ScSZ|La of fuel
0.8Sr
0.2MnO
3Fuel cell system
At first, preparation catalyst: take by weighing Ni (NO
3)
26H
2O 3.468g, Al (NO
3)
29H
2O 68.43g.Use deionized water dissolving, add glycine, wherein, the mol ratio (G/M of glycine and total metal ion
N+) than being 2: 1, after treating to dissolve fully, this solution under stirring condition 80 ℃ be heated into thick, spontaneous combustion in baking oven then, temperature is 240 ℃.The 800 ℃ of calcinings 5 hours in Muffle furnace of cooling back, grind into powder obtains NiO-Al
2O
3Powder.
Then, the preparation battery: take by weighing ScSZ powder 30g and NiO powder 45g, adding PVB 5.25g and an amount of ethanol take out behind the ball milling 24h, keep 80 ℃ of oven dry after ball milling 40min promptly get required anode composite granule.Take by weighing anode powder 0.3g, ScSZ 0.02g makes the base substrate that contains dielectric substrate by mould, in 1500 ℃ of sintering (can earlier with anode prereduction).Negative electrode is made into slurry, with spray gun negative electrode is sprayed on bath surface, 1150 ℃ of sintered cathodes get final product (if anode prereduction then must be led to protective atmosphere such as N
2, He etc.).
Secondly, prepare anode-catalyzed coating, get the NiO-Al that above-mentioned steps makes
2O
3Powder 1g adds the 10ml isopropyl alcohol, 0.6ml glycerine, and 2ml ethylene glycol takes out after advancing high-energy ball milling 50min, is sprayed on anode surface with spray gun, heating, drying.Catalytic Layer thickness is 15 μ m.
At last, carry out with methane, oxygen (4: 1) is the testing solid oxide fuel cell of fuel, adopts the four point probe structure, and the reactor outside adds sleeve pipe.As can be seen from Figure 1, be not coated with NiO-Al
2O
3During Catalytic Layer, in the time of 750 ℃, power density is 75mW/cm
2, and be coated with NiO-Al
2O
3After the Catalytic Layer, in the time of 750 ℃, power density is 293mW/cm
2The good results are evident for anode-catalyzed coating.
Embodiment 2: with methane, steam is the Ni+ScSz|ScSz|La of fuel
0.8Sr
0.2MnO
3Fuel cell system.
At first, preparation catalyst: take by weighing Ni (NO
3)
26H
2O 3.964g, Al (NO
3)
29H
2O 67.70g.Use deionized water dissolving, add glycine, wherein, the mol ratio (G/M of glycine and total metal ion
N+) than being 2.5: 1, after treating to dissolve fully, this solution under stirring condition 100 ℃ be heated into thick, spontaneous combustion in baking oven then, temperature is 230 ℃.The 850 ℃ of calcinings 6 hours in Muffle furnace of cooling back, grind into powder obtains NiO-Al
2O
3Powder.
The preparation battery methods is with embodiment 1.
Secondly, prepare anode-catalyzed coating, 1gNiO-Al
2O
3Powder adds the 18ml isopropyl alcohol, 1.0ml glycerine, and 3.5ml ethylene glycol takes out after advancing high-energy ball milling 40min, is sprayed on anode surface with spray gun, heating, drying.Catalytic Layer thickness is 10 μ m.
Then, carry out with methane, steam (2: 1) is the testing solid oxide fuel cell of fuel, adopts the four point probe structure, and the reactor outside adds sleeve pipe.As can be seen from Figure 2, during Catalytic Layer, in the time of 750 ℃, power density is not 103mW/cm
2, and after being coated with Catalytic Layer, in the time of 750 ℃, power density is 281mW/cm
2
Embodiment 3: with methane, carbon dioxide is the Ni+ScSZ|ScSZ|La of fuel
0.8Sr
0.2MnO
3Fuel cell system
At first, preparation catalyst: take by weighing Ru (NO
3)
31.988g, Ce (NO
3)
46H
2O 23.46g.Use deionized water dissolving, add glycine, wherein, the mol ratio (G/M of glycine and total metal ion
N+) than being 3: 1, after treating to dissolve fully, this solution under stirring condition 110 ℃ be heated into thick, spontaneous combustion in baking oven then, temperature is 200 ℃.The 800 ℃ of calcinings 7 hours in Muffle furnace of cooling back, grind into powder obtains RuO
2-CeO
2Powder.
The preparation battery, the catalyst coat method is with embodiment 1.
Then, carry out with methane, carbon dioxide (2: 1) is the testing solid oxide fuel cell of fuel, adopts the four point probe structure, and the reactor outside adds sleeve pipe.As can be seen from Figure 3, when not being coated with Catalytic Layer, in the time of 750 ℃, power density is 60mW/cm
2, and after being coated with Catalytic Layer, in the time of 750 ℃, power density is 259mW/cm
2
Embodiment 4: with methane, carbon dioxide is the Ni+ScSZ|ScSZ|La of fuel
0.8Sr
0.2MnO
3Fuel cell system
At first, preparation catalyst: take by weighing Ni (NO
3)
26H
2O 3.468g, Al (NO
3)
39H
2O 61.81g, La (NO
3)
20.9973g, Li (NO
3)
20.2307g, use deionized water dissolving, add glycine, wherein, the mol ratio (G/M of glycine and total metal ion
N+) than being 2: 1, after treating to dissolve fully, this solution under stirring condition 110 ℃ be heated into thick, spontaneous combustion in baking oven then, temperature is 200 ℃.The 900 ℃ of calcinings 5 hours in Muffle furnace of cooling back, grind into powder obtains NiO-Al
2O
3-La
2O
3-Li
2The O powder.
The preparation battery methods is with embodiment 1.
Secondly, prepare anode-catalyzed coating, 1gNiO-Al
2O
3-La
2O
3-Li
2The O powder adds the 12ml isopropyl alcohol, 0.8ml glycerine, and 3ml ethylene glycol takes out after advancing high-energy ball milling 45min, is sprayed on anode surface with spray gun, heating, drying.Catalytic Layer thickness is 20 μ m.
Then, carry out with methane, carbon dioxide (2: 1) is the testing solid oxide fuel cell of fuel, adopts the four point probe structure, and the reactor outside adds sleeve pipe.As can be seen from Figure 4, when not being coated with Catalytic Layer, in the time of 750 ℃, power density is 60mW/cm
2, and after being coated with Catalytic Layer, in the time of 750 ℃, power density is 294mW/cm
2
Embodiment 5: with methane, oxygen is the Ni+ScSZ|ScSZ|La of fuel
0.8Sr
0.2MnO
3The stability test of fuel cell system
The preparation catalyst, battery, the catalyst coat method is with embodiment 1.
Then, carry out with methane, oxygen is the Solid Oxide Fuel Cell stability test of fuel, adopts the four point probe structure, and the reactor outside adds sleeve pipe.As can be seen from Figure 5, be coated with Catalytic Layer after, with methane, oxygen (4: 1) is that the Solid Oxide Fuel Cell of fuel kept in 70 minutes stable in the time of 850 ℃.
Embodiment 6: be the Ni+ScSZ|ScSZ|La of fuel with methane
0.8Sr
0.2MnO
3The stability test of fuel cell system
The preparation catalyst, battery, the catalyst coat method is with embodiment 1.
Then, carrying out with the pure methane is the Solid Oxide Fuel Cell stability test of fuel, adopts the four point probe structure, and the reactor outside adds sleeve pipe.As can be seen from Figure 6, be coated with Catalytic Layer after, in the time of 850 ℃ be that the Solid Oxide Fuel Cell of fuel kept stable in 150 minutes with methane.
Embodiment 7: with methane, oxygen is the Ni+ScSZ|ScSZ|La of fuel
0.8Sr
0.2MnO
3The stability test of fuel cell system
The preparation catalyst, battery, the catalyst coat method is with embodiment 4.
Then, carry out with methane, oxygen is the Solid Oxide Fuel Cell stability test of fuel, adopts the four point probe structure, and the reactor outside adds sleeve pipe.As can be seen from Figure 7, be coated with Catalytic Layer after, in the time of 850 ℃ be that the Solid Oxide Fuel Cell of fuel kept stable in 70 minutes with methane.
Claims (8)
1. an anode loading functional coating is the solid oxide fuel battery system of main fuel with methane, it is characterized in that anode outer surface load one deck catalyst coatings at battery, when being main fuel with methane, partial oxidation and interior reforming reaction according to methane produce carbon monoxide and hydrogen, increase the anti-carbon performance of anode; The catalyst of wherein said catalyst coatings is NiO-Al
2O
3Or RuO
2-Al
2O
3In a kind of, or at NiO-Al
2O
3The middle La that adds
2O
3And/or Li
2O; When described anode-catalyzed coated catalysts is NiO-Al
2O
3Or RuO
2-Al
2O
3In a kind of the time, the content of metal Ni or Ru is that the percentage by weight that accounts for the catalyst total amount is 5%-10% in the catalyst; When described anode-catalyzed coated catalysts is NiO-Al
2O
3The middle La that adds
2O
3And/or Li
2During O, the content of metal Ni is that the percentage by weight that accounts for the catalyst total amount is 5%-10% in the catalyst, La
2O
3And Li
2The content of O is that the percentage by weight that accounts for the catalyst total amount is 3-10%; The thickness of wherein said anode-catalyzed coating is 10 μ m-20 μ m..
2. battery system according to claim 1, the operating temperature that it is characterized in that described fuel cell system is 600-1000 ℃.
3. battery system according to claim 1 is characterized in that described battery adopts tubular type or planar cells configuration, and battery configuration adopts anode support type or electrolyte-supporting type.
4. battery system according to claim 1, the electrolyte that it is characterized in that described battery adopt a kind of in samarium oxide doping of cerium oxide, gadolinium oxide doping of cerium oxide, yttrium stable zirconia, lanthanum strontium gallium magnesium or the scandium zirconium; Negative electrode adopts a kind of in lanthanum strontium manganese, lanthanum strontium scandium manganese, barium strontium ferro-cobalt, lanthanum strontium ferro-cobalt, lanthanum strontium cobalt or the strontium scandium cobalt; Anode adopts electrolyte/nickel composite anode, lanthanum strontium scandium manganese or lanthanum strontium chromium manganese Ca-Ti ore type anode.
5. battery system according to claim 1, the preparation method who it is characterized in that anode coated catalysts in the battery system is: the nitrate that takes by weighing various metals by stoichiometric proportion, use deionized water dissolving, add glycine, after treating to dissolve fully, this solution under stirring condition 80-120 ℃ be heated into thick, spontaneous combustion in baking oven then, temperature is 200-300 ℃; 800-1000 ℃ of calcining 5-10 hour in Muffle furnace of cooling back, grind into powder makes catalyst.
6. battery system according to claim 5, the addition that it is characterized in that glycine are that the mol ratio of metal ion total in glycine and the metal nitrate is 2: 1-3: 1.
7. battery system according to claim 1 is characterized in that described anode-catalyzed coating adopts the preparation of fully-automatic ultrasonic sprayed on membrane method.
8. battery system according to claim 1 is characterized in that described is to add oxygen, steam or carbon dioxide in the main fuel with methane.
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| CN104064792B (en) * | 2014-06-25 | 2016-03-09 | 合肥工业大学 | A kind of high-temperature electrolysis water vapour Simultaneous Oxidation methane is for the method for fuel |
| CN106159288B (en) * | 2015-04-22 | 2019-03-08 | 中国科学院物理研究所 | A kind of Ni base anode material, preparation method and the purposes of anti-carbon |
| CN105244523B (en) * | 2015-08-28 | 2018-04-03 | 山西大学 | A kind of SOFC with anti-carbon function |
| CN109755597A (en) * | 2019-01-08 | 2019-05-14 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | A kind of large-area flat-plate type solid oxide fuel cell palladium oxide composite cathode and preparation method thereof |
| CN112762468B (en) * | 2019-10-21 | 2022-04-08 | 中国石油化工股份有限公司 | Method for catalytic combustion of volatile organic compounds |
| CN111477880B (en) * | 2020-03-05 | 2021-07-27 | 浙江工业大学 | CeOx/RuO2(iii) MC and CeOx/RuO2Preparation and application of composite nanosheet material |
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