CN113745531A - High-performance solid oxide electrolytic cell and preparation method thereof - Google Patents
High-performance solid oxide electrolytic cell and preparation method thereof Download PDFInfo
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- 239000007787 solid Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 46
- 239000000758 substrate Substances 0.000 claims abstract description 46
- 239000010935 stainless steel Substances 0.000 claims abstract description 37
- 239000003792 electrolyte Substances 0.000 claims abstract description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- 239000011148 porous material Substances 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 16
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 10
- 230000008014 freezing Effects 0.000 claims abstract description 10
- 238000007710 freezing Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 229910002484 Ce0.9Gd0.1O1.95 Inorganic materials 0.000 claims description 8
- 229910002138 La0.6Sr0.4CoO3 Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 239000011267 electrode slurry Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000002103 nanocoating Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910021281 Co3O4In Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000000446 fuel Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 9
- 229910021320 cobalt-lanthanum-strontium oxide Inorganic materials 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 229910002080 8 mol% Y2O3 fully stabilized ZrO2 Inorganic materials 0.000 description 3
- 229910002075 lanthanum strontium manganite Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 2
- 229910002127 La0.6Sr0.4Co0.2Fe0.8O3 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- 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
- H01M4/8605—Porous electrodes
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- 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
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8668—Binders
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
- H01M8/1226—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material characterised by the supporting layer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/126—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing cerium oxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides a high-performance solid oxide electrolytic cell and a preparation method thereof, relating to the technical field of fuel cells. The high-performance solid oxide electrolytic cell comprises a bipolar plate, a stainless steel substrate, a hydrogen electrode, an electrolyte film, a paste layer and a honeycomb active oxygen electrode from bottom to top. The preparation method of the invention adopts a freezing method, can realize the control of the aperture and the pore density of the electrode, has the porosity up to 75 percent, is easy to form straight pores with small curvature, ensures that oxygen generated by electrolysis is easier to release, and increases active sites capable of participating in reaction. The porous cerium oxide-based paste layer is adopted to bond the oxygen electrode and the electrolyte, so that the contact between interfaces can be effectively improved, and the electrolytic performance of the electrolytic cell is improved. The metal substrate is used as a support body, the thickness of the electrode and the electrolyte is correspondingly reduced, the overall resistance of the electrolytic cell is reduced, and the performance of the electrolytic cell can be effectively improved by combining the electrolytic cell with the honeycomb oxygen electrode with high porosity and low resistance.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a high-performance solid oxide electrolytic cell and a preparation method thereof.
Background
(1) The traditional solid oxide electrolytic cell takes La1-xSrxMnO3 (LSM) as an anode, the working temperature is generally above 800 ℃, and the higher temperature not only causes high manufacturing difficulty, but also greatly limits the selection range of materials. Therefore, the development prospect of the intermediate-temperature solid oxide electrolytic cell which works at the temperature of about 600 ℃ is wider.
(2) Under the condition of medium temperature, the performances of an electrolyte, an oxygen electrode and a hydrogen electrode are reduced due to the reduction of the temperature, and the oxygen electrode is more obviously influenced by the reduction of the temperature due to larger reaction activation energy, so that the development of a high-performance oxygen electrode is more important for improving the performance of an electrolytic cell.
The traditional oxygen electrode is usually prepared on a half cell directly by adopting a high-temperature sintering mode, and the high temperature of more than 1000 ℃ is needed for ensuring the good combination between the electrode and the electrolyte. Therefore, the anode has the problems of single pore structure, low porosity, short three-phase interface, few activated reaction sites and the like. Therefore, the development of new high performance oxygen electrodes is the key to the preparation of high performance solid oxide electrolytic cells.
In view of the above, it is desirable to provide a high performance solid oxide electrolytic cell and a method for manufacturing the same to solve the above technical problems.
Disclosure of Invention
The invention aims to provide a high-performance solid oxide electrolytic cell and a preparation method thereof.
In order to realize the purpose, the following technical scheme is provided:
the invention provides a high-performance solid oxide electrolytic cell, which comprises a bipolar plate, a stainless steel substrate, a hydrogen electrode, an electrolyte film, a paste layer and a honeycomb active oxygen electrode from bottom to top.
Further, the bipolar plate is a ferritic stainless steel bipolar plate, and/or the stainless steel substrate is a ferritic stainless steel substrate, the ferritic stainless steel is stable in titanium/niobium, and the Cr content is 17.5-18.5%.
Further, the electrolyte film is a cerium oxide-based electrolyte film, and/or the paste layer is a cerium oxide-based paste layer, and the cerium oxide-based constituent is Ce0.9Gd0.1O1.95And Co3O4In which C ise0.9Gd0.1O1.9598% of Co3O4Accounting for 2%, measured in mole fraction.
Further, the high-performance solid oxide electrolytic cell comprises at least one of the following modes:
the first method is as follows: the bipolar plate is provided with a flow passage for gas to flow;
the second method comprises the following steps: la coated with conductive electrons on the stainless steel substrate0.6Sr0.4Co0.2Fe0.8O3An active oxide coating.
Further, the hydrogen electrode is NiO and Ce0.9Gd0.1O1.95The prepared composite electrode contains 50% of NiO powder and Ce0.9Gd0.1O1.95The powder is 50% by volume.
Further, the honeycomb active oxygen electrode is Y0.08Zr0.92O2Honeycomb stent and La0.6Sr0.4CoO3Composite electrode consisting of an active nanocoating, wherein La0.6Sr0.4CoO327% of Y0.08Zr0.92O2Accounting for 73 percent by mass.
Furthermore, the center of the stainless steel substrate is a porous area, the edge of the stainless steel substrate is a non-porous area, and the bipolar plate is bonded with the non-porous area of the stainless steel substrate.
Furthermore, the holes of the porous area penetrate through two sides of the stainless steel substrate, the hole diameter is 50-250 μm, and the ratio of the hole area to the stainless steel substrate area is 40-65%.
Furthermore, the thickness of the stainless steel substrate is 50-250 μm, the thickness of the hydrogen electrode is 10-25 μm, and the porosity is 30-60%; the thickness of the electrolyte film is 10-20 μm, and the density is more than or equal to 95%; the thickness of the paste layer is 0.2-1 μm, and the porosity is 5-20%; the thickness of the honeycomb active oxygen electrode is 50-250 μm, and the porosity is 50-75%.
The invention also provides a preparation method of the high-performance solid oxide electrolytic cell in any technical scheme, which comprises the following steps:
carrying out optical processing on the stainless steel substrate raw material to obtain a porous stainless steel substrate; coating the hydrogen electrode slurry on a stainless steel substrate, and performing high-temperature sintering at the temperature of 750-1050 ℃ to form a hydrogen electrode with a porous structure;
coating an electrolyte on the hydrogen electrode layer, and sintering at a high temperature of 950 ℃ in a neutral atmosphere to form a sufficiently dense electrolyte film while preventing the stainless steel substrate from being excessively oxidized;
preparing honeycomb bracket slurry, pouring the slurry into a mold, placing on a cold source to form a cold source at the bottom and form a temperature gradient at the top in an atmospheric environment, and freezing for 20-40 min; drying in a vacuum box for 18-30h, and then sintering at 1200-1600 ℃ to form an electrode bracket; the ice crystals grow along the direction of the temperature gradient, thereby forming pores; the larger temperature gradient causes the growth rate of ice crystals in the material to be different, the lower the temperature, the smaller and more the pores are, the lower the temperature is, the dense layer is at the bottom and the pore structure similar to honeycomb is at the top;
bonding the electrode support with an electrolyte film through a paste layer, and sintering at high temperature of 750-1050 ℃;
preparing an active layer solution, injecting the active layer solution into the honeycomb-shaped electrode bracket in a nano mode, depositing the active layer solution on the inner surface of the channel, and drying for 4-8 hours at the temperature of 30-40 ℃; finally, sintering at high temperature of 750-1050 ℃ to load the active layer on the honeycomb-shaped electrode bracket; repeating the steps until the mass fraction requirement is met, and obtaining the high-performance solid oxide electrolytic cell.
Compared with the prior art, the high-performance solid oxide electrolytic cell and the preparation method thereof provided by the invention have the following beneficial effects:
(1) the porous oxygen electrode is prepared by a freezing method, different temperature gradients can be formed by adjusting the temperature of a cold source, so that the control of the aperture and the pore density of the electrode is realized, and the porosity can reach 75 percent at most. Meanwhile, due to the characteristic that ice crystals grow along the temperature gradient during freezing, straight holes with small tortuosity are easily formed, so that oxygen generated by electrolysis is easier to release active sites which can participate in reaction and increase.
(2) The porous cerium oxide-based paste layer is adopted to bond the oxygen electrode and the electrolyte, so that the contact between interfaces can be effectively improved, and the electrolytic performance of the electrolytic cell is improved.
(3) The metal substrate is used as a support body, the thickness of the electrode and the electrolyte is correspondingly reduced, the overall resistance of the electrolytic cell is reduced, and the performance of the electrolytic cell can be effectively improved by combining the electrolytic cell with the honeycomb oxygen electrode with high porosity and low resistance.
This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the detailed description. This summary is not intended to identify key features or essential features of the disclosure, nor is it intended to be used to limit the scope of the disclosure.
Drawings
The foregoing and other objects, features and advantages of the disclosure will be apparent from the following more particular descriptions of exemplary embodiments of the disclosure as illustrated in the accompanying drawings wherein like reference numbers generally represent like parts throughout the exemplary embodiments of the disclosure.
Fig. 1 shows a schematic of the structure of a high performance solid oxide electrolytic cell of an embodiment of the present invention.
Reference numerals:
1-a bipolar plate; 2-stainless steel substrate; a 3-hydrogen electrode; 4-electrolyte thin film; 5-paste layer; 6-honeycomb active oxygen electrode.
Detailed Description
Embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
The term "include" and variations thereof as used herein is meant to be inclusive in an open-ended manner, i.e., "including but not limited to". Unless specifically stated otherwise, the term "or" means "and/or". The term "based on" means "based at least in part on". The terms "one example embodiment" and "one embodiment" mean "at least one example embodiment". The term "another embodiment" means "at least one additional embodiment". The terms "first," "second," and the like may refer to different or the same object. Other explicit and implicit definitions are also possible below.
As shown in fig. 1, the present example provides a high-performance solid oxide electrolytic cell comprising a bipolar plate 1, a stainless steel substrate 2, a hydrogen electrode 3, an electrolyte membrane 4, a paste layer 5 and a honeycomb active oxygen electrode 6 from bottom to top.
Specifically, the bipolar plate 1 of the present embodiment is a ferritic stainless steel bipolar plate, the stainless steel substrate 2 is a ferritic stainless steel substrate, and the bipolar plate 1 and the stainless steel substrate 2 are made of the same material. Preferably, the ferritic stainless steel of the present example is titanium/niobium stabilized and contains Cr in an amount of 17.5-18.5%. Preferably, the stainless steel substrate 2 is coated with an electron-conducting La0.6Sr0.4Co0.2Fe0.8O3An active oxide coating.
Alternatively, the stainless steel substrate 2 has a porous region in the center and non-porous regions at the edges, and the bipolar plate 1 is bonded to the non-porous regions of the stainless steel substrate 2. The bipolar plate 1 is provided with flow channels for gas to flow through.
Further, the electrolyte thin film 4 is a cerium oxide-based electrolyte thin film, the paste layer 5 is a cerium oxide-based paste layer, and the cerium oxide-based constituent is Ce0.9Gd0.1O1.95And Co3O4Wherein GDC occupies 98%，Co3O4The composition and the compounding ratio of the cerium oxide-based paste layer of this example were the same as those of the cerium oxide-based electrolyte thin film, in terms of a mole fraction of 2%.
The hydrogen electrode 3 is NiO and Ce0.9Gd0.1O1.95(GDC) wherein the NiO powder is 50% and the GDC powder is 50% in volume fraction.
The honeycomb active oxygen electrode 6 is Y0.08Zr0.92O2(8 YSZ) Honeycomb support and La0.6Sr0.4CoO3The composite electrode consists of an active nano coating, wherein the LSC accounts for 27 percent, and the 8YSZ accounts for 73 percent, and the mass fraction is measured.
Further, the thickness of the stainless substrate 2 of the present embodiment is 50 to 250 μm, the pores of the porous region penetrate both sides of the stainless substrate 2, the pore size is 50 to 250 μm, and the ratio of the pore area to the area of the stainless substrate 2 is 40 to 65%. The thickness of the hydrogen electrode 3 is 10-25 μm, and the porosity is 30-60%; the thickness of the electrolyte film 4 is 10-20 μm, and the density is more than or equal to 95%; the thickness of the paste layer 5 is 0.2-1 μm, and the porosity is 5-20%; the thickness of the honeycomb active oxygen electrode 6 is 50-250 μm, and the porosity is 50-75%.
The embodiment also provides a preparation method of the high-performance solid oxide electrolytic cell, which comprises the following steps:
1) carrying out optical processing on the stainless steel substrate raw material to obtain a porous stainless steel substrate 2; coating the hydrogen electrode slurry on a stainless steel substrate 2, and performing high-temperature sintering at the temperature of 750-1050 ℃ to form a hydrogen electrode 3 with a porous structure;
2) coating an electrolyte on the hydrogen electrode 3 layer and sintering at a high temperature of 950 ℃ in a neutral atmosphere to form a sufficiently dense electrolyte film 4 while preventing the stainless steel substrate 2 from being excessively oxidized;
3) preparing honeycomb bracket slurry, pouring the slurry into a mold, placing on a cold source to form a cold source at the bottom and form a temperature gradient at the top in an atmospheric environment, and freezing for 20-40 min; drying in a vacuum box for 18-30h, and then sintering at 1200-1600 ℃ to form an electrode bracket; the ice crystals grow along the direction of the temperature gradient, thereby forming pores; the larger temperature gradient causes the growth rate of ice crystals in the material to be different, the lower the temperature, the smaller and more the pores are, the lower the temperature is, the dense layer is at the bottom and the pore structure similar to honeycomb is at the top;
4) the electrode bracket is bonded with the electrolyte film 4 through the paste layer 5 and is sintered at high temperature of 750-1050 ℃;
5) preparing an active layer solution, injecting the active layer solution into the honeycomb-shaped electrode bracket in a nano mode, depositing the active layer solution on the inner surface of the channel, and drying for 4-8 hours at the temperature of 30-40 ℃; finally, sintering at high temperature of 750-1050 ℃ to load the active layer on the honeycomb-shaped electrode bracket; repeating the steps until the mass fraction requirement is met, and obtaining the high-performance solid oxide electrolytic cell.
In particular, the amount of the solvent to be used,
the sintering temperature in step 1) is preferably 900 ℃.
The sintering temperature in step 2) is preferably 950 ℃.
The slurry in the step 3) is preferably Y0.08Zr0.92O2(8 YSZ) slurry, although materials that achieve the same effect may be selected in other embodiments, the freezing time is preferably 30min, the drying time is preferably 24h, and the sintering time is preferably 1400 ℃. The step 3) is specifically as follows: preparing 8YSZ slurry, pouring the slurry into a mold, placing on a cold source to make the bottom be a cold source and the top be an atmospheric environment to form a temperature gradient, and freezing for 30 min. Drying in a vacuum box for 24h, and then sintering at a high temperature of 1400 ℃ to form the electrode support. The ice crystals grow in the direction of the temperature gradient, thereby forming pores. The larger temperature gradient causes the growth rate of ice crystals in the material to be different, the lower the temperature, the smaller and the more the pores are, the dense layer is at the low temperature part of the bottom, and the pore structure similar to a honeycomb is at the top.
The sintering temperature in the step 4) is preferably 900 ℃, and the step 4) is specifically as follows: the 8YSZ electrode support is bonded with the cerium oxide-based electrolyte through the cerium oxide-based paste layer, and is sintered at high temperature of 900 ℃.
The preferable active layer solution in the step 5) is La0.6Sr0.4CoO3(LSC), the drying temperature is 35 ℃, the drying time is 6h, and the sintering temperature is 900 ℃. The step 4) is specifically as follows: configuration La0.6Sr0.4CoO3Nano injecting the active layer solution into the honeycomb bracket, and drying for 6 hours at 35 ℃ after the LSC solution is deposited on the inner surface of the channel; finally, the LSC active layer was loaded onto the honeycomb support by high temperature sintering at 900 ℃. Repeating the steps until the mass fraction requirement is met, and obtaining the high-performance solid oxide electrolytic cell.
The high-performance solid oxide electrolytic cell and the preparation method thereof have the following advantages:
(1) the porous oxygen electrode is prepared by a freezing method, different temperature gradients can be formed by adjusting the temperature of a cold source, so that the control of the aperture and the pore density of the electrode is realized, and the porosity can reach 75 percent at most. Meanwhile, due to the characteristic that ice crystals grow along the temperature gradient during freezing, straight holes with small tortuosity are easily formed, so that oxygen generated by electrolysis is easier to release active sites which can participate in reaction and increase.
(2) The porous cerium oxide-based paste layer is adopted to bond the oxygen electrode and the electrolyte, so that the contact between interfaces can be effectively improved, and the electrolytic performance of the electrolytic cell is improved.
(3) The metal substrate is used as a support body, the thickness of the electrode and the electrolyte is correspondingly reduced, the overall resistance of the electrolytic cell is reduced, and the performance of the electrolytic cell can be effectively improved by combining the electrolytic cell with the honeycomb oxygen electrode with high porosity and low resistance.
Having described embodiments of the present disclosure, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terms used herein were chosen in order to best explain the principles of the embodiments, the practical application, or technical improvements to the techniques in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Claims (10)
1. A high-performance solid oxide electrolytic cell is characterized by comprising a bipolar plate (1), a stainless steel substrate (2), a hydrogen electrode (3), an electrolyte film (4), a paste layer (5) and a honeycomb active oxygen electrode (6) from bottom to top.
2. The high performance solid oxide electrolysis cell according to claim 1, wherein said bipolar plate (1) is a ferritic stainless steel bipolar plate and/or the stainless steel substrate (2) is a ferritic stainless steel substrate, said ferritic stainless steel being titanium/niobium stable with a Cr content of 17.5-18.5%.
3. The high performance solid oxide electrolytic cell according to claim 1, wherein the electrolyte membrane (4) is a cerium oxide-based electrolyte membrane, and/or the paste layer (5) is a cerium oxide-based paste layer, and the cerium oxide-based constituent is Ce0.9Gd0.1O1.95And Co3O4In which Ce is0.9Gd0.1O1.9598% of Co3O4Accounting for 2%, measured in mole fraction.
4. The high performance solid oxide electrolysis cell of claim 1, comprising at least one of:
the first method is as follows: a flow channel for gas to flow is arranged on the bipolar plate (1);
the second method comprises the following steps: la coated with conductive electrons on the stainless steel substrate (2)0.6Sr0.4Co0.2Fe0.8O3An active oxide coating.
5. The high performance solid oxide electrolysis cell according to claim 1, wherein the hydrogen electrode (3) is NiO and Ce0.9Gd0.1O1.95The prepared composite electrode contains 50% of NiO powder and Ce0.9Gd0.1O1.95The powder is 50% by volume.
6. The high performance solid oxide electrolysis cell of claim 1, wherein said cell is characterized byThe honeycomb active oxygen electrode (6) is Y0.08Zr0.92O2Honeycomb stent and La0.6Sr0.4CoO3Composite electrode consisting of an active nanocoating, wherein La0.6Sr0.4CoO327% of Y0.08Zr0.92O2Accounting for 73 percent by mass.
7. The high performance solid oxide electrolysis cell according to claim 1, wherein said stainless steel substrate (2) has a porous area in the center and non-porous areas at the edges, and said bipolar plate (1) is bonded to the non-porous areas of said stainless steel substrate (2).
8. The high performance solid oxide electrolysis cell according to claim 7, wherein the pores of the porous area penetrate both sides of the stainless steel substrate (2) with a pore size of 50-250 μm and a ratio of the pore area to the area of the stainless steel substrate (2) is 40-65%.
9. The high performance solid oxide electrolysis cell according to any of claims 1 to 8, wherein the stainless steel substrate (2) has a thickness of 50 to 250 μm, the hydrogen electrode (3) has a thickness of 10 to 25 μm, and the porosity is 30 to 60%; the thickness of the electrolyte film (4) is 10-20 μm, and the density is more than or equal to 95 percent; the thickness of the paste layer (5) is 0.2-1 μm, and the porosity is 5-20%; the thickness of the honeycomb active oxygen electrode (6) is 50-250 μm, and the porosity is 50-75%.
10. A method of making a high performance solid oxide electrolytic cell as claimed in any one of claims 1 to 9, comprising the steps of:
carrying out optical processing on the stainless steel substrate raw material to obtain a porous stainless steel substrate (2); coating the hydrogen electrode slurry on a stainless steel substrate (2), and sintering at the temperature of 750-1050 ℃ to form a hydrogen electrode (3) with a porous structure;
coating an electrolyte on the hydrogen electrode (3) layer and sintering at a high temperature of 950 ℃ in a neutral atmosphere to form a sufficiently dense electrolyte film (4) while preventing the stainless steel substrate (2) from being excessively oxidized;
preparing honeycomb bracket slurry, pouring the slurry into a mold, placing on a cold source to form a cold source at the bottom and form a temperature gradient at the top in an atmospheric environment, and freezing for 20-40 min; drying in a vacuum box for 18-30h, and then sintering at 1200-1600 ℃ to form an electrode bracket; the ice crystals grow along the direction of the temperature gradient, thereby forming pores; the larger temperature gradient causes the growth rate of ice crystals in the material to be different, the lower the temperature, the smaller and more the pores are, the lower the temperature is, the dense layer is at the bottom and the pore structure similar to honeycomb is at the top;
the electrode bracket is bonded with the electrolyte film (4) through the paste layer (5) and sintered at high temperature of 750-;
preparing an active layer solution, injecting the active layer solution into the honeycomb-shaped electrode bracket in a nano mode, depositing the active layer solution on the inner surface of the channel, and drying for 4-8 hours at the temperature of 30-40 ℃; finally, sintering at high temperature of 750-1050 ℃ to load the active layer on the honeycomb-shaped electrode bracket; repeating the steps until the mass fraction requirement is met, and obtaining the high-performance solid oxide electrolytic cell.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024135343A1 (en) * | 2022-12-19 | 2024-06-27 | 太陽誘電株式会社 | Solid oxide fuel cell and production method for same |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020048699A1 (en) * | 2000-10-25 | 2002-04-25 | Steele Brian Charles Hilton | Fuel cells |
| US20070065701A1 (en) * | 2005-09-16 | 2007-03-22 | Cable Thomas L | Symmetrical, bi-electrode supported solid oxide fuel cell |
| JP2007324087A (en) * | 2006-06-05 | 2007-12-13 | Nippon Telegr & Teleph Corp <Ntt> | Ceria family buffer layer for air electrode of solid oxide fuel cell and its manufacturing method |
| JP2009263741A (en) * | 2008-04-28 | 2009-11-12 | Univ Of Yamanashi | High-temperature steam electrolytic cell |
| US20090286125A1 (en) * | 2008-04-03 | 2009-11-19 | The University Of Toledo | Bi-electrode supported solid oxide fuel cells having gas flow plenum channels and methods of making same |
| CN102134726A (en) * | 2011-01-10 | 2011-07-27 | 清华大学 | Flat plate type solid oxide electrolytic cell pile with novel sealed structure |
| US20120186976A1 (en) * | 2009-08-03 | 2012-07-26 | Commissariat à l'énergie atomique et aux énergies alternatives | Metal-supported electrochemical cell and method for fabricating same |
| CN103319182A (en) * | 2013-07-04 | 2013-09-25 | 清华大学 | High-performance solid oxide electrolytic tank support |
| US20150333342A1 (en) * | 2012-12-21 | 2015-11-19 | Commissariat A' L'Énergie Atomique et aux Énergies Alternatives | Electrical insulation and sealing surround for water electrolysis reactor (soec) or fuel cell (sofc) |
-
2021
- 2021-09-14 CN CN202111072583.5A patent/CN113745531A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020048699A1 (en) * | 2000-10-25 | 2002-04-25 | Steele Brian Charles Hilton | Fuel cells |
| US20070065701A1 (en) * | 2005-09-16 | 2007-03-22 | Cable Thomas L | Symmetrical, bi-electrode supported solid oxide fuel cell |
| JP2007324087A (en) * | 2006-06-05 | 2007-12-13 | Nippon Telegr & Teleph Corp <Ntt> | Ceria family buffer layer for air electrode of solid oxide fuel cell and its manufacturing method |
| US20090286125A1 (en) * | 2008-04-03 | 2009-11-19 | The University Of Toledo | Bi-electrode supported solid oxide fuel cells having gas flow plenum channels and methods of making same |
| JP2009263741A (en) * | 2008-04-28 | 2009-11-12 | Univ Of Yamanashi | High-temperature steam electrolytic cell |
| US20120186976A1 (en) * | 2009-08-03 | 2012-07-26 | Commissariat à l'énergie atomique et aux énergies alternatives | Metal-supported electrochemical cell and method for fabricating same |
| CN102134726A (en) * | 2011-01-10 | 2011-07-27 | 清华大学 | Flat plate type solid oxide electrolytic cell pile with novel sealed structure |
| US20150333342A1 (en) * | 2012-12-21 | 2015-11-19 | Commissariat A' L'Énergie Atomique et aux Énergies Alternatives | Electrical insulation and sealing surround for water electrolysis reactor (soec) or fuel cell (sofc) |
| CN103319182A (en) * | 2013-07-04 | 2013-09-25 | 清华大学 | High-performance solid oxide electrolytic tank support |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024135343A1 (en) * | 2022-12-19 | 2024-06-27 | 太陽誘電株式会社 | Solid oxide fuel cell and production method for same |
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