CN114361471A - Integrated independent catalytic layer, preparation method and application - Google Patents
Integrated independent catalytic layer, preparation method and application Download PDFInfo
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Abstract
The invention provides an integrated independent catalytic layer, a preparation method and application thereof. The integrated independent catalytic layer comprises a support body and an active component loaded on the support body. Wherein the support is a porous YSZ support; the active component is selected from spinel material containing no nickel, composite material of spinel and GDC oxide, metal containing no nickel and GDC oxide or CeO2One or more of the composite material and the anti-carbon deposition perovskite material; wherein the loading amount of the active component in the integrated independent catalytic layer is 50 wt% -60 wt%. The active component of the integrated independent catalytic layer and the support body have better combination degree, and the situation that the catalyst and the support body are separated from each other cannot occur.
Description
Technical Field
The invention relates to the field of fuel cells, in particular to an integrated independent catalytic layer for a solid oxide fuel cell, a preparation method of the integrated independent catalytic layer, application of the integrated independent catalytic layer in the solid oxide fuel cell, and the solid oxide fuel cell.
Background
Solid Oxide Fuel Cells (SOFC) are an efficient green energy conversion device, and compared with other types of fuel cells, the fuel is most flexibly used, and hydrocarbons such as methanol, propane, methane, ethanol and the like can be directly used as fuel. The nickel-based cermet is the most widely used anode material of the SOFC at present, and has higher catalytic activity and electrical conductivity on hydrogen and hydrocarbon fuels. However, when using hydrocarbon fuel, the carbon deposition on the nickel surface will destroy the cell structure and cause the cell performance to drop rapidly.
The stability of the SOFC can be effectively improved by directly loading a catalytic layer with good catalytic activity on hydrocarbon fuel on the surface of the traditional nickel-based cermet anode. To date, researchers have investigated the possibilities of various materials as direct-supported anode catalytic layers, including noble metal-based materials, nickel-based materials, copper-based materials, nickel-based alloy materials, spinel materials, and perovskite-based materials. Although the direct-supported catalyst layer has the advantage of simple preparation process, the direct support of the catalyst on the surface of the anode can damage the cell structure due to the mismatch of thermal expansion coefficients between the catalytic material and the anode material, and thus the stability of the cell is affected. In addition, the reforming reaction of hydrocarbon fuels is often accompanied by heat absorption and release, and even though the addition of a catalytic layer can alleviate the problem of anode carbon deposition, the higher heat during reforming can still change the local temperature of the whole anode, resulting in cell rupture due to temperature stress difference. The strontium-containing catalyst layer material can react with the Ni-YSZ anode substrate to generate a high-resistance insulating phase, although the battery current collection cannot be greatly influenced, the temperature stress can be generated on the catalyst layer-anode interface, and when the stress is large enough, the catalyst layer and the anode can be layered, so that the stability of the battery is influenced. How to solve the adverse effect of the direct supported catalyst layer on the battery is a problem to be solved urgently.
Disclosure of Invention
The present invention aims to address at least one of the above-mentioned deficiencies of the prior art. For example, an object of the present invention is to provide an integrated independent catalyst layer for a solid oxide fuel cell, in which active components of the integrated independent catalyst layer are well bonded to a support, and the catalyst and the support are not separated from each other. For another example, another object of the present invention is to provide an application of an integrated independent catalytic layer in a solid oxide fuel cell, which can further improve the performance and stability of the solid oxide fuel cell by using the integrated independent catalytic layer while solving a series of adverse effects on the cell caused by a direct supported catalytic layer.
In order to achieve the above object, a first aspect of the present invention provides an integrated independent catalytic layer for a solid oxide fuel cell, comprising a support and an active component supported on the support.
In some embodiments of the invention, the support is a porous YSZ support.
In some embodiments of the invention, the active component is selected from the group consisting of a nickel-free spinel material, spinel, and GDC oxygenComposite material of compound, nickel-free metal and GDC oxide and/or CeO2And anti-carbon deposition perovskite material. Wherein the loading amount of the active component in the integrated independent catalytic layer is 53.5 wt% -60 wt%.
According to the present invention, in the composite material of spinel and GDC oxide, spinel is a spinel material containing no nickel.
In some embodiments of the invention, the method of making the integrated independent catalytic layer comprises:
s2, dissolving an active component source in a solvent to obtain an intermediate solution;
s3, contacting the intermediate solution with a second reagent to obtain a precursor solution;
s4, carrying out dipping treatment on the support body through the precursor solution to obtain a dipped support body;
and S5, calcining the impregnated supporting body to obtain the integrated independent catalytic layer.
In some embodiments of the present invention, the preparation method of the support comprises the steps of mixing YSZ powder with a first reagent, tabletting, and calcining, wherein the first reagent is one or more selected from starch and graphite pore former.
In some embodiments of the invention, the mass ratio of the YSZ powder to the first reagent is (11-12): (9-10).
According to the invention, the YSZ powder is yttria-stabilized zirconia; the graphite pore-forming agent can be spherical graphite; the spherical graphite and starch in the present invention are not limited strictly, and those skilled in the art can select the spherical graphite and starch according to actual situations, such as commonly available spherical graphite and starch, for example, corn starch.
The tabletting method and conditions are not particularly limited in the present invention, and those skilled in the art can select suitable instruments and tabletting conditions according to actual conditions. For example, a tablet press is used to compress sheets having a diameter of 20mm at 200 MPa.
The method and conditions for calcination in the present invention are not particularly limited, and those skilled in the art can select the calcination according to the actual conditions. For example, calcination at 1300 degrees Celsius for 5 hours yields a porous YSZ support with a diameter of about 15 mm.
In the invention, the pore diameter of the prepared porous YSZ support body is 3-10 μm.
In some embodiments of the invention, the active component is selected from Cu1.3Mn1.7O4、MnFe2O4、Mn1.5Co1.5O4-GDC、Sr2Fe1.3Co0.2Mo0.5O6-δ、Cu-CeO2And Ag-GDC.
According to the invention, the active component Sr2Fe1.3Co0.2Mo0.5O6-δIn the above, δ is less than 6.
According to the present invention, GDC in the above active ingredient means GDC oxide, and the GDC oxide of the present invention is Gd0.1Ce0.9O1.95-δIn the formula, the value range of delta is less than 1.95.
According to the invention, Mn1.5Co1.5O4GDC is the corresponding active component oxide precursor obtained after adding active component source and other reagents and calcining, wherein Mn1.5Co1.5O4And the mass ratio of GDC to GDC is (3-7): (7-3).
According to the invention, Cu-CeO2Is a corresponding active component oxide precursor obtained after adding active component sources and other reagents and calcining, wherein Cu and CeO2The mass ratio of (3-7): (7-3).
According to the invention, Ag-GDC is a corresponding active component oxide precursor obtained by adding active component sources and other reagents and calcining, wherein the mass ratio of Ag to GDC is (3-7): (7-3).
In some embodiments of the present invention, in step S2, the active component source is at least two of lanthanum nitrate, strontium nitrate, cerium nitrate, cobalt nitrate, copper nitrate, iron nitrate, manganese nitrate, silver nitrate, gadolinium nitrate, and ammonium molybdate.
In some embodiments of the present invention, in step S2, the solvent is water and ethanol at a volume ratio of 4-5: 1.
In some embodiments of the present invention, in step S2, the active component source in the intermediate solution provides a total metal ion molar concentration of 0.5-1 mol/L.
In some embodiments of the invention, in step S3, the second agent is selected from one or more of citric acid and citric acid monohydrate.
In some embodiments of the present invention, in step S3, the molar ratio of the second reagent to the total metal ions in the precursor solution is 1.5-2: 1.
According to the present invention, the total metal ions refer to the molar amount of all metal ions in the active component source added in step S2.
In some embodiments of the present invention, in step S3, the intermediate solution is contacted with the second reagent and then hermetically mixed at 60 to 80 ℃.
In some embodiments of the present invention, in step S4, the precursor solution may be immersed into the support with a pipette to obtain an immersed support loaded with the precursor solution.
In some embodiments of the present invention, in step S5, the conditions of the calcination treatment include: the calcining temperature is 900-1100 ℃, and the calcining time is 5-10 h.
In accordance with the present invention, the supports were successfully loaded with active ingredients, referring to a pre-and post-comparison graph of loading the porous YSZ supports with active ingredients as shown in fig. 2.
In some embodiments of the invention, the method of making the integrated independent catalytic layer comprises:
1) mixing YSZ powder and a first reagent in a mass ratio of 11:9, tabletting and calcining to obtain a support body;
2) dissolving an active component source in a solvent to obtain an intermediate solution;
3) contacting the intermediate solution with a second reagent to obtain a precursor solution;
4) dipping the support body by the precursor solution to obtain a dipped support body;
5) and calcining the impregnated supporting body to obtain the integrated independent catalytic layer.
In some embodiments of the invention, the method of making the integrated independent catalytic layer comprises:
(1) uniformly mixing YSZ powder with a starch or graphite pore-forming agent, pressing into a sheet by using a tablet press, and calcining in a muffle furnace to form a porous support body with certain mechanical strength;
(2) dissolving an active component source in a solvent, mixing and adding citric acid monohydrate to obtain a catalyst precursor solution;
(3) and loading the prepared catalyst precursor solution into the porous support body by using a liquid-transferring gun through a dipping process, and calcining in a muffle furnace to obtain the integrated independent catalyst layer.
A second aspect of the present invention provides a method for preparing an integrated independent catalytic layer for a solid oxide fuel cell, comprising the steps of:
s1, mixing YSZ powder with a first reagent, tabletting and calcining to obtain a support body;
s2, dissolving an active component source in a solvent to obtain an intermediate solution;
s3, contacting the intermediate solution with a second reagent to obtain a precursor solution;
s4, carrying out dipping treatment on the support body through the precursor solution to obtain a dipped support body;
and S5, calcining the impregnated supporting body to obtain the integrated independent catalytic layer.
In some embodiments of the present invention, in step S1, the first reagent is selected from one or more of starch and graphite pore former.
In some embodiments of the present invention, in step S1, the mass ratio of the YSZ powder to the first reagent is (11-12): (9-10).
According to the invention, the YSZ powder is yttria-stabilized zirconia; the graphite pore-forming agent can be spherical graphite; the spherical graphite and the starch in the invention are not strictly limited, and can be selected by those skilled in the art according to actual conditions, and can be commonly used spherical graphite or starch, such as corn starch.
The tabletting method and conditions are not particularly limited in the present invention, and those skilled in the art can select suitable instruments and tabletting conditions according to actual conditions. For example, a tablet press is used to compress sheets having a diameter of 20mm at 200 MPa.
The method and conditions for calcination in the present invention are not particularly limited, and those skilled in the art can select the calcination according to the actual conditions. For example, calcination at 1300 degrees Celsius for 5 hours yields a porous YSZ support with a diameter of about 15 mm.
In the invention, the pore diameter of the prepared porous YSZ support body is 3-10 μm.
In some embodiments of the present invention, in step S2, the active component source is at least two of lanthanum nitrate, strontium nitrate, cerium nitrate, cobalt nitrate, copper nitrate, iron nitrate, manganese nitrate, silver nitrate, gadolinium nitrate, and ammonium molybdate.
In some embodiments of the present invention, in step S2, the solvent is water and ethanol at a volume ratio of 4-5: 1.
In some embodiments of the present invention, in step S2, the active component source in the intermediate solution provides a total metal ion molar concentration of 0.5-1 mol/L.
In some embodiments of the invention, in step S3, the second agent is selected from one or more of citric acid and citric acid monohydrate.
In some embodiments of the present invention, in step S3, the molar ratio of the second reagent to the total metal ions in the precursor solution is 1.5-2: 11.
According to the present invention, the total metal ions refer to the molar amount of all metal ions in the active component source added in step S2.
In some embodiments of the present invention, in step S3, the intermediate solution is contacted with the second reagent and then hermetically mixed at 60 to 80 ℃.
In some embodiments of the present invention, in step S4, the precursor solution may be immersed into the support with a pipette to obtain an immersed support loaded with the precursor solution.
In some embodiments of the present invention, in step S5, the conditions of the calcination treatment include: the calcining temperature is 900-1100 ℃, and the calcining time is 5-10 h.
In some embodiments of the present invention, the integrated independent catalytic layer obtained in step S5 has an active component loading amount of 53.5 wt% to 60 wt%.
According to the invention, the active component is selected from a nickel-free spinel material, a composite of spinel and GDC oxide, a nickel-free metal and GDC oxide or CeO2And anti-carbon deposition perovskite material.
According to the present invention, in the composite material of spinel and GDC oxide, spinel is a spinel material containing no nickel.
According to the invention, the active component is selected from Cu1.3Mn1.7O4、MnFe2O4、Mn1.5Co1.5O4-GDC、Sr2Fe1.3Co0.2Mo0.5O6-δ、Cu-CeO2And Ag-GDC.
According to the invention, the active component Sr2Fe1.3Co0.2Mo0.5O6-δIn (1),δis less than 6.
According to the present invention, GDC in the above active ingredient means GDC oxide, and GDC oxide is Gd0.1Ce0.9O1.95-δIn the formula, the value range of delta is less than 1.95.
According to the invention, Mn1.5Co1.5O4GDC is the corresponding active component oxide precursor obtained after addition of reagents such as active component sources and calcination, wherein,Mn1.5Co1.5O4and the mass ratio of GDC to GDC is (3-7): (7-3).
According to the invention, Cu-CeO2Is a corresponding active component oxide precursor obtained after adding active component sources and other reagents and calcining, wherein Cu and CeO2The mass ratio of (3-7): (7-3).
According to the invention, Ag-GDC is a corresponding active component oxide precursor obtained by adding active component sources and other reagents and calcining, wherein the mass ratio of Ag to GDC is (3-7): (7-3).
The third aspect of the present invention provides an application of the integrated independent catalytic layer according to the first aspect or the integrated independent catalytic layer prepared by the preparation method according to the second aspect in a solid oxide fuel cell, especially in a conventional Ni-YSZ anode-supported solid oxide fuel cell using hydrocarbon as fuel.
According to the present invention, referring to fig. 1, a solid oxide fuel cell comprises a cathode, an electrolyte between the anode and the cathode, an anode, and an integrated independent catalytic layer outside the anode and in close proximity or close proximity to the anode. In some embodiments, the integrated independent catalytic layer is separated from the anode of the cell, and the integrated independent catalytic layer and the anode of the cell can be adhered by using a conductive adhesive.
In a fourth aspect of the invention, a solid oxide fuel cell is provided, comprising a cathode, an electrolyte, an anode, and the integrated independent catalytic layer of the first aspect or the integrated independent catalytic layer prepared in the second aspect. Similarly, referring also to fig. 1, the electrolyte is located between the anode and the cathode, and the integrated independent catalytic layer is located outside the anode and in close proximity or close proximity to the anode. In some embodiments, the integrated independent catalytic layer is separated from the anode of the cell, and the integrated independent catalytic layer and the anode of the cell can be adhered by using a conductive adhesive.
Compared with the prior art, the beneficial effects of the present disclosure can include at least one of the following:
1) the integrated independent catalyst layer is applied to the traditional solid oxide fuel cell (such as Ni-YSZ anode support type) taking hydrocarbon as fuel, so that the performance and stability of the cell can be further improved while a series of adverse effects (such as separation and peeling of the catalyst layer and the cell anode) brought by a direct-loading catalyst layer on the cell are solved, and the stable operation of the solid oxide fuel cell in the hydrocarbon fuel is ensured;
2) the catalyst and the support body in the integrated independent catalyst layer have better combination degree, and the situation that the catalyst and the support body are separated from each other cannot occur;
3) the integrated independent catalyst layer has high carbon deposition resistance, and the reduction of the catalytic capability of the catalyst layer due to carbon deposition is avoided.
Drawings
Fig. 1 is a schematic structural view of the integrated independent catalytic layer of the present invention after being used in a solid oxide fuel cell;
FIG. 2 is a front-to-back comparison of the loading of active components on porous YSZ supports of the invention;
FIG. 3 is a graph comparing the stability of example 1 of the present invention and comparative example 1.
Detailed Description
The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer.
In the following examples, YSZ powder is a conventional product available from Ningbo Softow energy technologies, Inc.; the spherical graphite is conventional commercial graphite produced by a certain company, and the diameter of the spherical graphite is 15 mu m; the rest of the reagents or instruments are not indicated by manufacturers, and are all conventional products which can be obtained by commercial routes.
Example 1
(A) Preparation of porous YSZ support
Uniformly mixing YSZ powder with 40 wt% of spherical graphite and 5 wt% of corn starch to obtain a mixture; and weighing 0.3g of the mixture, performing compression molding by using a tablet press machine under 200MPa by using a tablet pressing die, and calcining for 5 hours at 1300 ℃ in a muffle furnace to obtain the porous YSZ support body with the pore diameter of 3-10 mu m.
(B)Cu-CeO2Preparation of catalyst precursor solution
According to Cu and CeO2In a molar ratio of 1: 1, weighing copper nitrate and cerium nitrate according to a volume ratio of 4: 1, dissolving the mixture by using water and ethanol as solvents, adding citric acid monohydrate after the copper nitrate and the cerium nitrate are completely dissolved, wherein the amount of the added citric acid monohydrate is determined by that the molar ratio of the citric acid monohydrate to total metal ions (the sum of copper ions and cerium ions) is 1.5: 1, hermetically heating and stirring the obtained solution at 80 ℃ for 20min to ensure that the solution is uniformly mixed to finally obtain the Cu-CeO2A catalyst precursor solution.
(C) Integrated Cu-CeO2Preparation of independent catalytic layer
Dipping method is adopted to use a liquid transfer gun to transfer Cu-CeO2And dropwise adding the catalyst precursor solution onto a porous YSZ support until the solution is not absorbed any more, drying at 60 ℃ for 60min, repeating the steps until the dropwise added solution is not absorbed any more, and then transferring into a muffle furnace to calcine at 850 ℃ for 3 h.
The steps of dipping and calcining are continuously repeated until the loaded Cu-CeO2The amount reached 53.5 wt% giving an integrated independent catalytic layer a 1.
Example 2
(A) Preparation of porous YSZ support
Uniformly mixing YSZ powder with 25 wt% of spherical graphite and 20 wt% of corn starch to obtain a mixture; and weighing 0.25g of the mixture, performing compression molding by using a tablet press machine under 200MPa by using a tablet pressing die, and calcining for 5 hours at 1300 ℃ in a muffle furnace to obtain the porous YSZ support body with the pore diameter of 3-10 mu m.
(B)Mn1.5Co1.5O4Preparation of GDC catalyst precursor solution
According to Mn1.5Co1.5O4Weighing gadolinium nitrate, cerium nitrate, manganese nitrate and cobalt nitrate according to the molar ratio of 6:4 to GDC, wherein the volume ratio of gadolinium nitrate to cerium nitrate to manganese nitrate to cobalt nitrate is 4: 1, dissolving in water and ethanol as solventAfter the nitrate is completely dissolved, adding citric acid monohydrate, wherein the amount of the added citric acid monohydrate is determined in such a way that the molar ratio of the citric acid monohydrate to total metal ions (the sum of manganese ions, cobalt ions, gadolinium ions and cerium ions) is 1.5: 1, sealing, heating and stirring the obtained solution at 80 ℃ for 20min to ensure that the solution is uniformly mixed, and finally obtaining Mn1.5Co1.5O4And GDC catalyst precursor solution.
(C) Integrated Mn1.5Co1.5O4Preparation of a GDC independent catalytic layer
Mn is added by dipping method with a liquid-transfering gun1.5Co1.5O4Dropwise adding the GDC catalyst precursor solution onto a porous YSZ support until the solution is not absorbed any more, drying at 60 ℃ for 60min, repeating the steps until the dropwise added solution is not absorbed any more, and then transferring into a muffle furnace to calcine at 1000 ℃ for 3 h.
The impregnation and calcination steps are repeated until the Mn loading is reached1.5Co1.5O4The amount of GDC reached 55.6 wt%, giving an integrated independent catalytic layer a 2.
Example 3
(A) Preparation of porous YSZ support
Uniformly mixing YSZ powder with 30 wt% of spherical graphite and 15 wt% of corn starch to obtain a mixture; and weighing 0.3g of the mixture, performing compression molding by using a tablet press machine under 200MPa by using a tablet pressing die, and calcining for 5 hours at 1350 ℃ in a muffle furnace to obtain a porous YSZ support body with the pore diameter of 3-10 mu m.
(B) Preparation of Ag-GDC catalyst precursor solution
According to the molar ratio of Ag to GDC of 3: weighing silver nitrate, gadolinium nitrate and cerium nitrate according to a volume ratio of 4: 1, dissolving the mixture by using water and ethanol as solvents, adding citric acid monohydrate after the silver nitrate, the gadolinium nitrate and the cerium nitrate are completely dissolved, wherein the amount of the added citric acid monohydrate is determined by that the molar ratio of the citric acid monohydrate to total metal ions (the sum of silver ions, gadolinium ions and cerium ions) is 2:1, sealing, heating and stirring the obtained solution at 80 ℃ for 20min to ensure that the solution is uniformly mixed, and finally obtaining the Ag-GDC catalyst precursor solution.
(C) Preparation of integrated Ag-GDC independent catalyst layer
And dropwise adding the Ag-GDC catalyst precursor solution onto a porous YSZ support body by using a liquid-transfering gun by adopting an impregnation method until the solution is not absorbed any more, drying at 60 ℃ for 60min, repeating the steps until the dropwise added solution is not absorbed any more, and then transferring into a muffle furnace to calcine at 800 ℃ for 3 h.
The above impregnation and calcination steps were repeated until the amount of supported Ag-GDC reached 52.3 wt%, to obtain an integrated independent catalytic layer a 3.
Example 4
(A) Preparation of porous YSZ support
Uniformly mixing YSZ powder with 27 wt% of spherical graphite and 28 wt% of corn starch to obtain a mixture; and weighing 0.28g of the mixture, performing compression molding by using a tablet press machine under 200MPa by using a tablet pressing die, and calcining for 5 hours at 1300 ℃ in a muffle furnace to obtain the porous YSZ support body with the pore diameter of 3-10 mu m.
(B)MnFe2O4Preparation of catalyst precursor solution
According to MnFe2O4Weighing ferric nitrate and manganese nitrate according to the molar ratio of the elements, wherein the volume ratio is 4: 1, dissolving the mixture by using water and ethanol as solvents, adding citric acid monohydrate after the ferric nitrate and the manganese nitrate are completely dissolved, wherein the amount of the added citric acid monohydrate is determined by that the molar ratio of the citric acid monohydrate to total metal ions (the sum of iron ions and manganese ions) is 1.5: 1, hermetically heating and stirring the obtained solution at 80 ℃ for 20min to ensure that the solution is uniformly mixed, and finally obtaining MnFe2O4A catalyst precursor solution.
(C) Integrated MnFe2O4Preparation of independent catalytic layer
Adopting a dipping method to mix MnFe with a liquid transfer gun2O4And dropwise adding the catalyst precursor solution onto a porous YSZ support until the solution is not absorbed any more, drying at 60 ℃ for 60min, repeating the steps until the dropwise added solution is not absorbed any more, and then transferring into a muffle furnace to calcine at 1100 ℃ for 3 h.
Repeat without interruptionThe steps of dipping and calcining are carried out until the supported MnFe2O4In an amount of up to 58.2 wt%, to give an integrated independent catalytic layer a 4.
Example 5
(A) Preparation of porous YSZ support
Uniformly mixing YSZ powder with 32 wt% of spherical graphite and 13 wt% of corn starch to obtain a mixture; and weighing 0.35g of the mixture, performing compression molding by using a tablet press machine under 200MPa by using a tablet pressing die, and calcining for 5 hours at 1300 ℃ in a muffle furnace to obtain the porous YSZ support body with the pore diameter of 3-10 mu m.
(B)Sr2Fe1.3Co0.2Mo0.5O6-δPreparation of catalyst precursor solution
According to Sr2Fe1.3Co0.2Mo0.5O6-δWeighing strontium nitrate, ferric nitrate, cobalt nitrate and ammonium molybdate according to the molar ratio of the elements, wherein the volume ratio is 4: 1, dissolving the nitrate by using water and ethanol as solvents, adding citric acid monohydrate after the nitrate is completely dissolved, wherein the amount of the added citric acid monohydrate is determined by that the molar ratio of the citric acid monohydrate to total metal ions (the sum of strontium ions, iron ions, cobalt ions and molybdenum ions) is 2:1, sealing, heating and stirring the obtained solution at 80 ℃ for 20min to ensure that the solution is uniformly mixed, and finally obtaining the Sr2Fe1.3Co0.2Mo0.5O6-δA catalyst precursor solution.
(C) Integrated Sr2Fe1.3Co0.2Mo0.5O6-δPreparation of independent catalytic layer
Sr is transferred by a liquid transfer gun by adopting an immersion method2Fe1.3Co0.2Mo0.5O6-δAnd dropwise adding the catalyst precursor solution onto a porous YSZ support until the solution is not absorbed any more, drying at 60 ℃ for 60min, repeating the steps until the dropwise added solution is not absorbed any more, and then transferring into a muffle furnace to calcine at 1100 ℃ for 3 h.
The steps of impregnation and calcination are repeated until the supported Sr is reached2Fe1.3Co0.2Mo0.5O6-δIn an amount of up to 60 wt%, to give an integrated independent catalytic layer a 5.
Test example
Testing the battery: the anode-supported cell for testing was a commercially produced anode-supported half cell from the Guangdong tide state tricyclic group, and the anode structure was: Ni-YSZ/Ni-ScSZ/ScSZ/GDC, and LSCF as cathode.
The test method comprises the following steps: the integrated independent catalytic layers a1 to a5 obtained in the above examples 1 to 5 were tightly attached to the anode of the test cell and adhered by a conductive adhesive; before testing, the cells were first tested at 800 ℃ with H2Reducing for 3h, and then testing; pure methanol is used as fuel gas, and N is used by adopting a bubbling method2As carrier gas, the concentration of fuel gas introduced into the cell is controlled to be 60%, the test method and the content are the same as the test of the conventional solid oxide fuel cell, constant current discharge is carried out at 750 ℃, and the stability of the cell in methanol fuel is tested.
The test results are: as shown in fig. 3, the blank test cell without the integrated independent catalytic layer continuously decayed during the constant current discharge, while the test cell with the integrated independent catalytic layer a1 did not significantly decay in the stable operation during the constant current discharge; the test cells with the integrated independent catalytic layers a 2-a 5 were also more stable than the blank test cells without catalytic layers in the constant current discharge process.
The results show that the integrated independent catalyst layer can effectively protect the battery from the destructive effects of carbon deposition and temperature stress caused by methanol cracking and reforming.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. An integrated independent catalytic layer for a solid oxide fuel cell, comprising a support and an active component supported on the support, wherein,
the support is a porous YSZ support;
the active component is selected from spinel material containing no nickel, composite material of spinel and GDC oxide, metal containing no nickel and GDC oxide and/or CeO2One or more of the composite material and the anti-carbon deposition perovskite material;
wherein the loading amount of the active component in the integrated independent catalytic layer is 50-60 wt%;
preferably, the preparation method of the integrated independent catalytic layer comprises the following steps:
s2, dissolving an active component source in a solvent to obtain an intermediate solution;
s3, contacting the intermediate solution with a second reagent to obtain a precursor solution;
s4, carrying out dipping treatment on the support body through the precursor solution to obtain a dipped support body;
and S5, calcining the impregnated supporting body to obtain the integrated independent catalytic layer.
2. The integrated independent catalytic layer of claim 1, wherein the preparation method of the support comprises the steps of mixing YSZ powder with a first reagent, tabletting and calcining, wherein the first reagent is one or more selected from starch and graphite pore-forming agents; preferably, the mass ratio of the YSZ powder to the first reagent is (11-12): (9-10).
3. The integrated independent catalytic layer according to claim 1 or 2, characterized in that the active component is selected from Cu1.3Mn1.7O4、MnFe2O4、Mn1.5Co1.5O4-GDC、Sr2Fe1.3Co0.2Mo0.5O6-δ、Cu-CeO2And Ag-GDC.
4. The integrated independent catalytic layer according to any one of claims 1 to 3, wherein in step S2, the active component sources are at least two of lanthanum nitrate, strontium nitrate, cerium nitrate, cobalt nitrate, copper nitrate, ferric nitrate, manganese nitrate, silver nitrate, gadolinium nitrate, and ammonium molybdate; and/or
The solvent is prepared by mixing the following components in a volume ratio of 4-5: 1, preferably, the molar concentration of the total metal ions provided by the active component source in the intermediate solution is 0.5-1 mol/L.
5. The integrated independent catalytic layer according to any one of claims 1 to 4, wherein in step S3, the second reagent is selected from one or more of citric acid and citric acid monohydrate; and/or
The molar ratio of the second reagent to the total metal ions in the precursor solution is 1.5-2: 1; and/or
The intermediate solution is contacted with a second reagent and then sealed and mixed at the temperature of 60-80 ℃.
6. The integrated independent catalytic layer according to any one of claims 1 to 5, wherein in step S5, the calcination treatment conditions include: the calcining temperature is 900-1100 ℃, and the calcining time is 5-10 h.
7. A method for preparing an integrated independent catalytic layer for a solid oxide fuel cell, comprising the steps of:
s1, mixing YSZ powder with a first reagent, tabletting and calcining to obtain a support body;
s2, dissolving an active component source in a solvent to obtain an intermediate solution;
s3, contacting the intermediate solution with a second reagent to obtain a precursor solution;
s4, carrying out dipping treatment on the support body through the precursor solution to obtain a dipped support body;
and S5, calcining the impregnated supporting body to obtain the integrated independent catalytic layer.
8. The method according to claim 7, wherein in step S1, the first reagent is selected from one or more of starch and graphite pore former; preferably, the mass ratio of the YSZ powder to the first reagent is (11-12): (9-10); and/or
In step S2, the active component sources are at least two of lanthanum nitrate, strontium nitrate, cerium nitrate, cobalt nitrate, copper nitrate, ferric nitrate, manganese nitrate, silver nitrate, gadolinium nitrate, and ammonium molybdate; the solvent is water and ethanol with a volume ratio of 4-5: 1, and the molar concentration of total metal ions provided by the active component source in the intermediate solution is 0.5-1 mol/L; and/or
In step S3, the second agent is selected from one or more of citric acid and citric acid monohydrate; the molar ratio of the second reagent to the total metal ions in the precursor solution is 1.5-2: 1; the intermediate solution is contacted with a second reagent and then sealed and mixed at the temperature of 60-80 ℃; and/or
In step S5, the conditions of the calcination treatment include: the calcining temperature is 800-1100 ℃, and the calcining time is 5-10 h.
9. The preparation method according to claim 7 or 8, wherein the loading amount of the active component in the integrated independent catalytic layer obtained in the step S5 is 50 wt% to 60 wt%.
10. An application of the integrated independent catalyst layer according to any one of claims 1 to 6 or the integrated independent catalyst layer prepared by the preparation method according to any one of claims 7 to 9 in a solid oxide fuel cell, in particular to an application in a traditional Ni-YSZ anode-supported solid oxide fuel cell taking hydrocarbon as fuel.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101803097A (en) * | 2007-07-19 | 2010-08-11 | 纳米动力公司 | Internal reforming solid oxide fuel cells |
| CN102903940A (en) * | 2012-10-22 | 2013-01-30 | 天津工业大学 | Asymmetric composite anode of microtuble-type solid oxide fuel cell and preparation method of asymmetric composite anode |
| CN104103838A (en) * | 2014-07-08 | 2014-10-15 | 华中科技大学 | Anode protection layer for solid oxide fuel cell, and preparation method and application of anode protection layer |
| CN105244523A (en) * | 2015-08-28 | 2016-01-13 | 山西大学 | Solid oxide fuel cell with anti-carbon function |
| CN105932304A (en) * | 2016-05-20 | 2016-09-07 | 辽宁石油化工大学 | Preparation method for solid oxide fuel cell anode |
-
2022
- 2022-01-10 CN CN202210022352.1A patent/CN114361471A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101803097A (en) * | 2007-07-19 | 2010-08-11 | 纳米动力公司 | Internal reforming solid oxide fuel cells |
| CN102903940A (en) * | 2012-10-22 | 2013-01-30 | 天津工业大学 | Asymmetric composite anode of microtuble-type solid oxide fuel cell and preparation method of asymmetric composite anode |
| CN104103838A (en) * | 2014-07-08 | 2014-10-15 | 华中科技大学 | Anode protection layer for solid oxide fuel cell, and preparation method and application of anode protection layer |
| CN105244523A (en) * | 2015-08-28 | 2016-01-13 | 山西大学 | Solid oxide fuel cell with anti-carbon function |
| CN105932304A (en) * | 2016-05-20 | 2016-09-07 | 辽宁石油化工大学 | Preparation method for solid oxide fuel cell anode |
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