CN115020716B - Fuel cell and preparation method of flat tube solid oxide fuel cell functional layer thereof - Google Patents
Fuel cell and preparation method of flat tube solid oxide fuel cell functional layer thereof Download PDFInfo
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- CN115020716B CN115020716B CN202111662116.8A CN202111662116A CN115020716B CN 115020716 B CN115020716 B CN 115020716B CN 202111662116 A CN202111662116 A CN 202111662116A CN 115020716 B CN115020716 B CN 115020716B
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- 239000000446 fuel Substances 0.000 title claims abstract description 26
- 239000007787 solid Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002346 layers by function Substances 0.000 title claims abstract description 11
- 239000010410 layer Substances 0.000 claims abstract description 144
- 239000003792 electrolyte Substances 0.000 claims abstract description 74
- 239000000843 powder Substances 0.000 claims abstract description 73
- 239000002994 raw material Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000005245 sintering Methods 0.000 claims abstract description 22
- 239000002270 dispersing agent Substances 0.000 claims abstract description 20
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 13
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 238000001125 extrusion Methods 0.000 claims abstract description 6
- 239000000314 lubricant Substances 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims description 34
- 238000007649 pad printing Methods 0.000 claims description 19
- 230000004888 barrier function Effects 0.000 claims description 18
- 238000007639 printing Methods 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 18
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 11
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 11
- 239000003085 diluting agent Substances 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 7
- 239000005751 Copper oxide Substances 0.000 claims description 7
- 229910052963 cobaltite Inorganic materials 0.000 claims description 7
- 229910000431 copper oxide Inorganic materials 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 6
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 6
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052706 scandium Inorganic materials 0.000 claims description 6
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims description 5
- 238000004364 calculation method Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 5
- 230000002093 peripheral effect Effects 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 3
- 239000008029 phthalate plasticizer Substances 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 abstract description 4
- 238000010146 3D printing Methods 0.000 abstract description 3
- 238000002347 injection Methods 0.000 abstract description 3
- 239000007924 injection Substances 0.000 abstract description 3
- 238000000462 isostatic pressing Methods 0.000 abstract description 3
- 239000004014 plasticizer Substances 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000003754 machining Methods 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 229910002080 8 mol% Y2O3 fully stabilized ZrO2 Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 229910052688 Gadolinium Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 229940116411 terpineol Drugs 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- PTIQFRFYSQUEOU-UHFFFAOYSA-N [Co]=O.[La] Chemical compound [Co]=O.[La] PTIQFRFYSQUEOU-UHFFFAOYSA-N 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010023 transfer printing Methods 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
Abstract
The invention relates to a fuel cell and a preparation method of a flat tube solid oxide fuel cell functional layer thereof, which relate to the technical field of fuel cells and comprise the following steps: mixing the support raw materials; adding liquid raw materials into the support powder raw materials, and mixing to obtain mixed raw materials; wherein the raw materials of the support body powder are 30-60% of nickel oxide powder and 30-70% of yttria-stabilized zirconia powder, and the liquid raw materials are 3-10% of pore-forming agent; the liquid raw materials comprise 3-35% of plasticizer, 0.5-15% of dispersing agent, 0.5-3% of defoaming agent and 0.5-15% of lubricant; and an anode support layer blank is prepared from the obtained mixed raw materials by adopting an extrusion molding method, an isostatic pressing method, an injection method, a grouting method or a 3D printing method, and the anode support layer blank has a hollow hole structure, so that the problems that the electrolyte layer used for sealing at the side edge of the produced support body is not easy to compact, the sealing performance is weakened and the like in the sintering process of the electrolyte layer of the traditional flat tube type solid oxide fuel cell are solved.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a fuel cell and a preparation method of a flat tube solid oxide fuel cell functional layer thereof.
Background
The invention relates to preparation of solid oxide fuel cell electrolyte, and a Solid Oxide Fuel Cell (SOFC) is a power generation device with high efficiency, no pollution and an all-solid structure, can adapt to various fuel gases and does not need an additional reforming device. The prior flat tube type solid oxide fuel cell with symmetrical structure mainly comprises a support body, an anode layer, an electrolyte layer, a barrier layer, a cathode layer and the like. The flat tube solid oxide fuel cell is formed by combining a flat plate type cell and a tubular cell, and is structurally characterized in that a hollow hole is formed in an anode supporting layer, and the hollow hole is provided with an opening end at the side surface of the anode supporting layer. The pad printer is a printing device suitable for plastic, toy, glass, metal, ceramic, electronic, IC sealing and the like, has simple process and has become a main method for printing and decorating the surfaces of various objects. The existing pad printing machine equipment improves the pad printing efficiency by increasing the number of pad printing rubber heads on the basis of the traditional pad printing equipment. Namely, similar pad printing patents pay attention to macro-viewing effects such as efficiency, definition, conductivity and the like of silk-screen patterns, and few microstructures such as uniformity, continuity, bulk density, high-temperature sintering density and the like of thickness of a micro-gel film after pad printing are involved. The existing solid oxide fuel cell electronic ceramic side printing is mainly in the modes of lifting, dipping, manual brushing and the like, and the following problems easily occur in the preparation process of the functional layer film: 1. the coating film is uneven, so that slurry is easy to accumulate; 2. after the electrolyte is burnt, the microcosmic lower functional layer structure is not compact enough; 3. the preparation efficiency is low, and the method is not suitable for mass production.
Disclosure of Invention
The invention aims to provide a novel preparation method of a flat tube type solid oxide fuel cell, which effectively solves the problems of the original preparation process in the background art and has the advantages of simplicity in operation, good universality, high product yield and safety, easiness in large-scale production and the like.
In order to achieve the above object, the present invention provides a method for preparing a flat tube solid oxide fuel cell functional layer, comprising the steps of:
step S1: mixing the support raw materials; adding liquid raw materials into the support powder raw materials, and mixing to obtain mixed raw materials; wherein the raw materials of the support body powder are 30-60% of nickel oxide powder and 30-70% of yttria-stabilized zirconia powder, and the liquid raw materials are 3-10% of pore-forming agent; the liquid raw materials comprise 3-35% of plasticizer, 0.5-15% of dispersing agent, 0.5-3% of defoaming agent and 0.5-15% of lubricant; preparing an anode support layer blank body by adopting an extrusion molding method, an isostatic pressing method, an injection method, a grouting method or a 3D printing method, wherein the anode support layer blank body has a hollow hole structure;
step S2: preparing a support: drying the anode support layer blank, and then sintering at 1000 ℃ to obtain the support body;
step S3: first machining: carrying out first machining on the support body, and machining the three-dimensional size of the support body to a set value;
step S4: preparing an active anode layer and an anode current collecting layer: setting nickel oxide or a mixture of copper oxide and yttria-stabilized zirconia on the upper surface of the support, setting metal oxide on the lower surface of the support, and sintering at 900 ℃ for 2h; an active anode layer is formed on the upper surface of the support body, and an anode current collecting layer is formed on the lower surface of the support body;
step S5: preparing an electrolyte layer: fixing a special fixture on pad printing equipment, fixing a support body on the special fixture, pouring the prepared electrolyte slurry into an oil cup of the pad printing equipment, starting to perform printing, preparing a first electrolyte layer on the upper surface of an active anode layer, preparing a second electrolyte layer on the peripheral surface of an anode current collecting layer, starting to perform side electrolyte layer printing, connecting the first electrolyte layer with the second electrolyte layer through the side electrolyte layer, and sintering at 1360 ℃ for 5 hours after printing is completed to achieve compactness;
step S6: preparing a barrier layer: setting cerium oxide on the upper surface of the first electrolyte layer, and sintering at 1360 ℃ for 5 hours; a barrier layer is formed on the upper surface of the support body;
step S7: preparing a cathode layer: and a lanthanum cobaltite perovskite is arranged on the upper surface of the barrier layer, and a cathode layer is formed on the upper surface of the support body.
As a further preferred aspect, the anode current collecting layer in the step S4 may be selected from a metal oxide which is easily reduced, such as nickel oxide; the mass ratio of the copper oxide to the yttria-stabilized zirconia mixture is 70%.
As a further preferred aspect, the step S5 further includes a step S51 of preparing electrolyte powder: the electrolyte layer material adopts bismuth oxide doped with yttrium and scandium rare earth elements, then corresponding electrolyte powder is weighed according to a chemical combination metering ratio, 100g of the electrolyte powder is added into a grinding tank, then 60g of cyclohexanone and 10g of surfactant S-1015 are respectively added, wherein the ratio of the electrolyte powder to the diluent is 1:0.6:0.1, the mixed solution is put into a cavitation machine for stirring for 5min, after the completion, 5g of dispersing agent 5027 is added, and the ratio of the powder to the dispersing agent is 1:0.05; and (3) placing the mixed solution into a cavitation machine, stirring for 5min, taking out after the mixed solution is finished, placing the mixed solution into a three-roll machine, grinding the mixed solution to be less than 2um, and ensuring that the solid content of the slurry is 57%.
As a further preferred aspect, the step S5 further includes a step S51 of preparing electrolyte powder: weighing corresponding 8YSZ powder according to a chemical combination metering ratio, adding 100g of 8YSZ powder into a grinding tank, then respectively adding 90g of terpineol serving as a diluent and 30g of S-15 serving as a surfactant, wherein the ratio of the powder to the diluent is 1:0.9:0.3, putting the mixed solution into a cavitation machine, stirring for 5min, taking out after the completion, and adding 10g of dispersing agent 5040, wherein the ratio of the dispersing agent to the powder is 1:0.1; and (3) placing the mixed solution into a cavitation machine, stirring for 5min, taking out after the mixed solution is finished, placing the mixed solution into a three-machine, and grinding the mixed solution to be less than 2um, wherein the solid content of the slurry is 41.5%.
As a further preferred aspect, the electrolyte layer material is manganese with a powder particle size D50 ranging from 0.6 to 1um, a calcium-doped nickel-based alloy, and a combination of the above materials.
As a further preferred aspect, the electrolyte layer material is a low temperature densification material with high sintering activity, such as zirconium oxide, bismuth oxide, cerium oxide, and combinations thereof doped with one or more different rare earth elements, such as yttrium, scandium, gadolinium, cerium, and the like.
As a further preferred aspect, the special fixture in step S5 refers to the international shore calculation method to select a flat bottom rubber head with a hardness of 20 degrees or a conical rubber head with a hardness of 40A degrees.
As a further preferred aspect, the cerium oxide is doped with neodymium rare earth element in the step S6, and the particle diameter D50 of the cerium oxide powder is in the range of 0.2 to 0.5um.
As a further preferred aspect, in the step S7, the lanthanum cobaltite perovskite is doped with a strontium rare earth element, and the powder particle diameter D50 of the lanthanum cobaltite perovskite is 0.2um.
A fuel cell comprises a functional layer obtained by the preparation method of the flat tube solid oxide fuel cell functional layer.
Compared with the prior art, the preparation technology of the invention has the following main advantages:
(1) The side printing thickness of the invention is more uniform, and the thickness deviation can be controlled within 2um.
(2) The pad printing film has higher stacking density, can reach higher density after high-temperature sintering, and is beneficial to sealing fuel in the support body.
(3) The thickness of the film can be accurately controlled, and the thickness of the film can be flexibly adjusted within the range of 3-10um according to actual needs.
(4) The height of the workbench is adjusted, so that printing of electronic ceramic plates with different specifications can be realized. The slurry storage oil cup prevents the slurry from being polluted, and also avoids the waste caused by slurry residue in the screen when the screen is cleaned.
(5) The printing non-uniformity and the stacking phenomenon before are avoided, the later manual repair process is reduced, the working efficiency is improved, the production cost is reduced, and the method is simple and easy to implement.
(6) An improved pad printing method is provided to solve the problems of efficiency and uniformity of preparing the side electrolyte membrane of the flat tube solid oxide fuel cell. The traditional pad printing is mainly used for pattern printing on the surface of an object, mainly solves the problems of pad printing efficiency, pattern definition and the like, and less relates to controlling the microstructure such as the thickness, film forming uniformity, sintering compactness and the like of a pad printing film. On the basis of the traditional pad printing method, the hardness of the pad printing rubber head is improved, the rubber head shape is optimized according to the substrate shape, meanwhile, each rubber head shape corresponds to different electronic paste formulas and other methods, the thickness of a film is accurately controlled to be accurately adjusted within the range of 3-10um, the deviation of the thickness of the film is within 2um, and the film after pad printing has higher stacking density and high density after high-temperature sintering.
Drawings
FIG. 1 is a schematic view of a flat tube solid oxide fuel cell of the present invention;
FIG. 2 is a 40A cone forming head structure diagram according to an embodiment of the present invention;
FIG. 3 is a diagram of a 20A molded plastic head according to a second embodiment of the present invention;
FIG. 4 is a view showing the effect of the electrolyte structure of the present invention;
fig. 5 is a view showing the effect of the cathode structure of the present invention.
1. A side electrolyte layer; 2. an active anode layer; 3. a first electrolyte layer; 4. a barrier layer; 5. a cathode layer; 6. an anode current collecting layer; 7. a second electrolyte layer; 8. a support body.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the description of the present invention, it should be understood that the directions or positional relationships indicated by the terms "upper", "lower", "front", "rear", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the apparatus or elements referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present invention. The terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature.
Referring to fig. 1 and 3, a method for preparing a fuel cell and a flat tube solid oxide fuel cell functional layer thereof includes: step S1: mixing the support raw materials; adding liquid raw materials into the support powder raw materials, and mixing to obtain mixed raw materials; wherein the raw materials of the support body powder are 30-60% of nickel oxide powder, 30-70% of yttrium oxide stabilized zirconia powder and 3-10% of pore-forming agent; 3-35% of a plasticizer, 0.5-15% of a dispersing agent, 0.5-3% of a defoaming agent and 0.5-15% of a lubricant; preparing an anode support layer blank body by adopting an extrusion molding method, an isostatic pressing method, an injection method, a grouting method or a 3D printing method from the obtained mixed raw materials, wherein the anode support layer blank body has a hollow hole structure;
step S2: preparing a support: drying the anode support layer blank, and then sintering at 1000 ℃ to obtain a support body;
step S3: first machining: carrying out first machining on the support body, and machining the three-dimensional size of the support body to a set value;
step S4: preparing an anode layer and an anode current collecting layer: setting nickel oxide or a mixture of copper oxide and yttria-stabilized zirconia on the upper surface of the support, setting metal oxide on the lower surface of the support, and sintering at 900 ℃ for 2h; the upper surface of the support body forms an anode layer, and the lower surface of the support body forms an anode current collecting layer;
step S5: preparing a first electrolyte layer, a side electrolyte layer, and a second electrolyte layer: fixing a special fixture on transfer printing equipment, fixing a support body on the special fixture, pouring prepared electrolyte slurry into an oil cup of the transfer printing equipment, starting to perform printing, preparing a first electrolyte layer (103) on the upper surface of an active anode layer, preparing a second electrolyte layer on the peripheral surface of an anode current collecting layer, starting to perform side electrolyte layer printing, connecting the first electrolyte layer with the second electrolyte layer through the side electrolyte layer, and sintering at 1360 ℃ for 5 hours after printing is completed to achieve compactness;
step S6: preparing a barrier layer: setting cerium oxide on the upper surface of the first electrolyte layer and sintering at 1360 deg.c for 5 hr; forming a barrier layer on the upper surface of the first electrolyte layer;
step S7: preparing a cathode layer: lanthanum cobaltite perovskite is arranged on the upper surface of the barrier layer, and a cathode layer is formed on the upper surface of the barrier layer.
Further, as a preferred embodiment, as shown in fig. 1, the anode current collector layer in step S4 may be selected from a metal oxide which is easily reduced, such as nickel oxide; the mass ratio of the copper oxide to the yttria-stabilized zirconia mixture is 70 percent.
Further, as a preferred embodiment, step S5 further includes step S51 of preparing electrolyte powder: the electrolyte layer material adopts bismuth oxide doped with yttrium and scandium rare earth elements, then corresponding electrolyte powder is weighed according to a chemical combination metering ratio, 100g of electrolyte powder is added into a grinding tank, then 60g of cyclohexanone and 10g of surfactant S-1015 are respectively added, wherein the ratio of the electrolyte powder to the diluent is 1:0.6:0.1, the mixed solution is put into a cavitation machine for stirring for 5min, after the completion, 5g of dispersing agent 5027 is added, and the ratio of the powder to the dispersing agent is 1:0.05; stirring the mixed solution in a cavitation machine for 5min, taking out the mixed solution after the mixed solution is completed, grinding the mixed solution in a three-roll machine until the solid content of slurry is 57 percent and the solid content of slurry is less than 2 mu m;
further, as a preferred embodiment, step S5 further includes step S51 of preparing electrolyte powder: weighing corresponding 8YSZ powder according to a chemical combination metering ratio, adding 100g of 8YSZ powder into a grinding tank, then respectively adding 90g of terpineol serving as a diluent and 30g of S-15 serving as a surfactant, wherein the ratio of the powder to the diluent is 1:0.9:0.3, putting the mixed solution into a cavitation machine, stirring for 5min, taking out after the completion, and adding 10g of dispersing agent 5040, wherein the ratio of the dispersing agent to the powder is 1:0.1; and (3) placing the mixed solution into a cavitation machine, stirring for 5min, taking out after the mixed solution is finished, placing the mixed solution into a three-machine, and grinding the mixed solution to be less than 2um, wherein the solid content of the slurry is 41.5%.
Further, as a preferred embodiment, the electrolyte layer material is manganese-doped nickel-based alloy with a powder particle size D50 ranging from 0.6 to 1um, calcium-doped nickel-based alloy, and a combination of the above materials.
Further, as a preferred embodiment, in the step S1 of mixing the support raw materials, the electrolyte layer material is a low-temperature densification material having high sintering activity, such as zirconium oxide, bismuth oxide, cerium oxide, and combinations thereof doped with one or more different rare earth elements, such as yttrium, scandium, gadolinium, and cerium.
Further, as a preferred embodiment, the special fixture in step S5 refers to the international shore calculation method to select a flat bottom rubber head with a hardness of 20 degrees or a 40A degree conical rubber head.
Further, as a preferred embodiment, in step S6, cerium oxide is doped with neodymium rare earth element, and the particle diameter D50 of the cerium oxide powder is in the range of 0.2-0.5um.
Further, as a preferred embodiment, in step S7, the lanthanum perovskite cobaltite is doped with a strontium rare earth element, and the powder particle diameter D50 of the lanthanum perovskite cobaltite is 0.2um.
According to the first embodiment, as shown in fig. 1-2: adding liquid raw materials into the support powder raw materials for mixing and pugging to obtain mixed pug; the components and the contents of the support powder raw materials are as follows:
nickel oxide powder 46%
46% of yttria stabilized zirconia powder
3% of starch pore-forming agent
The liquid raw materials comprise the following components in percentage by weight:
3% of di (2-ethylhexyl) phthalate plasticizer
0.5% of polyolefin dispersant
Defoaming agent 1%
Lubricant 0.5%
Preparing an anode support layer blank body by using the mixed raw materials obtained in the step (1) by adopting an extrusion molding method, wherein the blank body has a hollow hole structure; and drying the green body and sintering at 1000 ℃ to obtain the anode support.
Preparing an anode layer and an anode current collecting layer, wherein the anode layer is made of a mixture of copper oxide and yttria-stabilized zirconia, the mass ratio of yttria-stabilized zirconia powder is 70%, the anode current collecting layer can select nickel oxide which is an easily reduced metal oxide, the anode layer is prepared on a support body which is cleaned and dried, the anode layer is positioned on the upper surface of the support body, the anode current collecting layer is positioned on the lower surface of the support body, and the anode current collecting layer is sintered for 2 hours at 900 ℃.
Preparing electrolyte slurry, wherein the electrolyte layer is zirconium oxide doped with gadolinium and cerium rare earth elements, weighing corresponding 8YSZ powder according to the chemical combination metering ratio,
the formula comprises the following components: 100g of powder is added into a grinding tank, 90g of terpineol serving as a diluent and 30g of surfactant S-15 are respectively added, wherein the ratio of the powder to the diluent to the surfactant is 1:0.9:0.3, the mixed solution is put into a cavitation machine for stirring for 5min, after the mixed solution is finished, the mixed solution is taken out, and 10g of dispersing agent 5040 is added, wherein the ratio of the dispersing agent to the powder is 1:0.1. Stirring the mixed solution in a cavitation machine for 5min, taking out after the stirring is completed, grinding the mixed solution to less than 2um in a three-machine, wherein the solid content of the slurry is 41.5%;
preparing an electrolyte layer: fixing a special fixture on pad printing equipment, fixing a support body on the special fixture, selecting a conical forming rubber head with the hardness of 40A degrees by referring to an international Schottky degree calculation method, pouring electrolyte slurry which is prepared into an oil cup, starting to print a side electrolyte layer, preparing a first electrolyte layer on the surface of a first anode layer, preparing a second electrolyte layer on the peripheral surface of an anode current collecting layer, and sintering the first electrolyte layer and the second electrolyte layer at 1360 ℃ for 5 hours after printing is finished to achieve compactness. And a conical molding rubber head structure.
The second electrolyte 20A DEG molded rubber head structure is shown in figure 3.
The material of the barrier layer is cerium oxide doped with neodymium rare earth elements, the particle size D50 of powder is 0.2um, and the barrier layer is positioned on the surface of the electrolyte layer and sintered for 1h at 1300 ℃.
Preparing a cathode layer, wherein the cathode layer is made of strontium rare earth element doped lanthanum cobalt oxide perovskite, the particle size D50 of powder is 0.2, and the cathode layer is positioned on the surface of the barrier layer.
With reference to FIGS. 3-4, a second embodiment is shown
Adding liquid raw materials into the support powder raw materials for mixing and pugging to obtain mixed pug; the components and the contents of the support powder raw materials are as follows:
nickel oxide powder 46%
46% of yttria stabilized zirconia powder
3% of starch pore-forming agent
The liquid raw materials comprise the following components in percentage by weight:
3% of di (2-ethylhexyl) phthalate plasticizer
0.5% of polyolefin dispersant
Defoaming agent 1%
Lubricant 0.5%
2) Preparing an anode support layer blank body by using the mixed raw materials obtained in the step (1) by adopting an extrusion molding method, wherein the blank body has a hollow hole structure;
3) And drying the green body and sintering at 1000 ℃ to obtain the support body.
4) Preparing an anode layer and an anode current collecting layer, wherein the anode layer is made of a mixture of copper oxide and yttria-stabilized zirconia, the mass ratio of yttria-stabilized zirconia powder is 70%, the anode current collecting layer can select nickel oxide which is an easily reduced metal oxide, the anode layer is prepared on a support body which is cleaned and dried, the anode layer is positioned on the upper surface of the support body, the anode current collecting layer is positioned on the lower surface of the support body, and the anode current collecting layer is sintered for 2 hours at 900 ℃.
5) Preparing powder: the electrolyte layer is bismuth oxide doped with yttrium and scandium rare earth elements, corresponding electrolyte powder is weighed according to a chemical combination metering ratio, 100g of powder is added into a grinding tank, 60g of cyclohexanone and 10g of surfactant S-1015 are respectively added, wherein the ratio of the powder to the diluent to the surfactant is 1:0.6:0.1, the mixed solution is placed into a cavitation machine for stirring for 5min, after the completion, the mixed solution is taken out, and 5g of dispersing agent 5027 is added, wherein the ratio of the powder to the dispersing agent is 1:0.05. And (3) placing the mixed solution into a cavitation machine, stirring for 5min, taking out after the mixed solution is finished, placing the mixed solution into a three-roll machine, grinding the mixed solution to be less than 2um, and ensuring that the solid content of the slurry is 57%.
6) Preparing an electrolyte layer: the special fixture is fixed on pad printing equipment, the support body is fixed on the special fixture, a flat bottom rubber head with the hardness of 20 ℃ is selected by referring to an international Schottky degree calculation method, electrolyte slurry which is prepared is poured into an oil cup, printing is started, a first electrolyte layer is prepared on the surface of a first anode layer, a second electrolyte layer is prepared on the peripheral surface of an anode current collecting layer, the first electrolyte layer is not connected with the second electrolyte layer, and sintering is carried out for 5 hours at 1360 ℃ after printing is finished, so that the density is achieved.
7) The material of the barrier layer is cerium oxide doped with neodymium rare earth elements, the particle size D50 of the powder ranges from 0.2um to 0.5um, the barrier layer is positioned on the surface of the electrolyte layer, and the sintering is carried out for 1h at 1300 ℃.
8) Preparing a cathode layer, wherein the cathode layer is made of strontium rare earth element doped lanthanum cobalt oxide perovskite, the particle size D50 of the powder ranges from 0.2um to 0.5um, and the cathode layer is positioned on the surface of the barrier layer. The foregoing is merely illustrative of the preferred embodiments of the present invention and is not intended to limit the embodiments and scope of the present invention, and it should be appreciated by those skilled in the art that equivalent substitutions and obvious variations may be made using the description and drawings of the present invention, and all such variations are intended to be included in the scope of the present invention.
Claims (1)
1. The preparation method of the flat tube solid oxide fuel cell functional layer is characterized by comprising the following steps of:
s1, adding a liquid raw material into a support powder raw material to carry out mixing pugging to obtain a mixed pug;
the components and the contents of the support powder raw materials are as follows:
46% of nickel oxide powder,
46% of yttria stabilized zirconia powder,
3% of starch pore-forming agent;
the liquid raw materials comprise the following components in percentage by weight:
3% of di (2-ethylhexyl) phthalate plasticizer,
0.5% of polyolefin dispersant,
1% of defoaming agent,
0.5% of a lubricant;
s2, preparing an anode support layer blank body by using the mixed raw materials obtained in the step S1 by adopting an extrusion molding method, wherein the blank body has a hollow hole structure;
s3, drying the blank body, sintering at 1000 ℃ and obtaining a support body;
s4, preparing an anode layer and an anode current collecting layer, wherein the anode layer is made of a mixture of copper oxide and yttria-stabilized zirconia, the mass ratio of yttria-stabilized zirconia powder is 70%, the anode current collecting layer is made of nickel oxide, the anode layer is prepared on a cleaned and dried support, the anode layer is positioned on the upper surface of the support, the anode current collecting layer is positioned on the lower surface of the support, and the anode current collecting layer is sintered for 2 hours at 900 ℃;
s5, preparing powder: the electrolyte layer is bismuth oxide doped with yttrium and scandium rare earth elements, corresponding electrolyte powder is weighed according to a chemical combination metering ratio, 100g of powder is added into a grinding tank, 60g of cyclohexanone and 10g of surfactant S-1015 are respectively added, wherein the proportion of the powder to the diluent to the surfactant is 1:0.6:0.1, the mixed solution is placed into a cavitation machine for stirring for 5min, after the completion, 5g of dispersing agent 5027 is added, wherein the proportion of the powder to the dispersing agent is 1:0.05, the mixed solution is placed into the cavitation machine for stirring for 5min, after the completion, the mixed solution is placed into a three-roller machine for grinding to below 2um, and the solid content of slurry is 57%;
s6, preparing an electrolyte layer: fixing a special fixture on pad printing equipment, fixing a support on the special fixture, selecting a flat-bottom rubber head with the hardness of 20 ℃ according to an international Shore calculation method, pouring electrolyte slurry prepared by modulation into an oil cup, starting to perform printing, preparing a first electrolyte layer on the surface of a first anode layer, preparing a second electrolyte layer on the peripheral surface of an anode current collecting layer, and sintering at 1360 ℃ for 5 hours to achieve compactness after printing;
s7, preparing a barrier layer material which is cerium oxide doped with neodymium rare earth elements, wherein the particle size D50 of powder ranges from 0.2 to 0.5um, and the barrier layer is positioned on the surface of the electrolyte layer and sintered for 1h at 1300 ℃;
s8, preparing a cathode layer, wherein the cathode layer is made of strontium rare earth element doped lanthanum cobaltite perovskite, the powder particle size D50 is in the range of 0.2-0.5um, and the cathode layer is positioned on the surface of the barrier layer.
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