CN116454291B - Perovskite type proton ceramic fuel cell single-phase cathode material and preparation method thereof - Google Patents
Perovskite type proton ceramic fuel cell single-phase cathode material and preparation method thereof Download PDFInfo
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- CN116454291B CN116454291B CN202310478190.7A CN202310478190A CN116454291B CN 116454291 B CN116454291 B CN 116454291B CN 202310478190 A CN202310478190 A CN 202310478190A CN 116454291 B CN116454291 B CN 116454291B
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- 239000010406 cathode material Substances 0.000 title claims abstract description 26
- 239000000919 ceramic Substances 0.000 title claims abstract description 24
- 239000000446 fuel Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 84
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000002243 precursor Substances 0.000 claims abstract description 34
- 239000000843 powder Substances 0.000 claims abstract description 23
- 229910001960 metal nitrate Inorganic materials 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 238000005303 weighing Methods 0.000 claims abstract description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 14
- 229910002828 Pr(NO3)3·6H2O Inorganic materials 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 11
- 239000002001 electrolyte material Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 229910002940 BaZr0.1Ce0.7Y0.2O3 Inorganic materials 0.000 description 3
- 102000020897 Formins Human genes 0.000 description 3
- 108091022623 Formins Proteins 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000006257 cathode slurry Substances 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000004952 furnace firing Methods 0.000 description 1
- 238000001566 impedance spectroscopy Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229940036248 turpentine Drugs 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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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
- H01M4/88—Processes of manufacture
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/32—Thermal properties
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- C01—INORGANIC CHEMISTRY
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention discloses a perovskite type proton ceramic fuel cell single-phase cathode material, the chemical formula of which is BaPr 1‑x‑y Co x Ni y O 3 The preparation method comprises the following steps: s1, respectively weighing metal nitrates of Ba, pr, co and Ni according to the stoichiometric ratio of the materials, and weighing ethylenediamine tetraacetic acid and citric acid; s2, pouring metal nitrate into a beaker, adding deionized water, stirring at 80 ℃ until the solution is clear, adding ethylenediamine tetraacetic acid, slowly dropwise adding ammonia water until the ethylenediamine tetraacetic acid is dissolved, adding citric acid and ammonia water, regulating the pH value of the solution, and stirring until gel is formed; s3, placing the gel obtained in the step S2 into an oven, and drying at 280 ℃ for 5 hours until the gel dries to obtain a precursor; and S4, grinding the precursor in the step S3, and then placing the ground precursor into a muffle furnace to calcine the ground precursor in an air atmosphere to obtain cathode powder. The obtained cathode material has good electrochemical performance and thermal expansion coefficient matched with electrolyte, and has good stability.
Description
Technical Field
The invention relates to the technical field of fuel cell materials, in particular to a perovskite type proton ceramic fuel cell single-phase cathode material and a preparation method thereof.
Background
The Proton Ceramic Fuel Cell (PCFC) is a novel power generation device and has the advantages of high power generation efficiency, wide fuel application range, lower working temperature and the like. PCFCs require that the cathode material have good electrochemical properties while also having a coefficient of thermal expansion that matches that of the electrolyte material.
The cathode with excellent performance at present is mostly Co-based or Fe-based oxide, and the thermal expansion coefficient is far greater than that of the commonly used electrolyte material BaZr 0.1 Ce 0.7 Y 0.2 O 3 (BZCY) is poor in matching degree with the electrolyte, so that the cathode is not matched with the electrolyte easily, and separation phenomenon is generated. Based on BaCeO 3 And BaZrO 3 Cathode materials developed from commonly used PCFC electrolyte materials such as base oxides are relatively matched with the thermal expansion coefficient of the electrolyte, but have poor electrochemical performance. There are also methods of compounding Co-based or Fe-based oxide with an electrolyte material such as BZCY to use as a PCFC cathode by mechanical mixing or impregnation, in which it is desired to combine superior electrochemical properties with a thermal expansion coefficient matching with the electrolyte, but mechanical mixing easily causes non-uniformity of the cathode material, poor stability, etc., impregnation rule is a very time-consuming preparation process, and impregnation amount is difficult to further increase.
Disclosure of Invention
The invention aims to provide a perovskite type proton ceramic fuel cell single-phase cathode material and a preparation method thereof.
To achieve the above object, the present invention provides a perovskite type proton ceramic fuel cell single-phase cathode material with molecular formula of BaPr 1-x-y Co x Ni y O 3 (0≤x≤0.2,0≤y≤0.2)。
A preparation method of a perovskite type proton ceramic fuel cell single-phase cathode material comprises the following steps:
s1, respectively weighing metal nitrates of Ba, pr, co and Ni according to the stoichiometric ratio of the materials, and weighing ethylenediamine tetraacetic acid and citric acid;
s2, pouring metal nitrate into a beaker, adding deionized water, stirring at 80 ℃ until the solution is clear, adding ethylenediamine tetraacetic acid, slowly dropwise adding ammonia water until the ethylenediamine tetraacetic acid is dissolved, adding citric acid and ammonia water, regulating the pH value of the solution, and stirring until gel is formed;
s3, placing the gel obtained in the step S2 into an oven, and drying at 280 ℃ for 5 hours until the gel dries to obtain a precursor;
and S4, grinding the precursor in the step S3, and then placing the ground precursor into a muffle furnace to calcine the ground precursor in an air atmosphere to obtain cathode powder.
Preferably, in step S1, the metal nitrates of Ba, pr, co and Ni are Ba (NO 3 ) 2 、Pr(NO 3 ) 3 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O and Ni (NO) 3 ) 2 ·6H 2 O。
Preferably, in step S1, according to metal ions: ethylenediamine tetraacetic acid: citric acid = 1:1:1.5 (molar ratio), ethylenediamine tetraacetic acid and citric acid were weighed.
Preferably, in step S2, the pH of the solution is adjusted to 8 and the stirring temperature is 80 ℃.
Preferably, in step S4, the calcination temperature is 1100 ℃.
Therefore, the perovskite type proton ceramic fuel cell single-phase cathode material and the preparation method thereof are adopted by the invention, and the perovskite type proton ceramic fuel cell single-phase cathode material is prepared by mixing the base material BaPrO 3 The B site of the PCFC single-phase cathode material is developed by a Co and Ni Co-doping method, has good electrochemical performance and stability, and has a thermal expansion coefficient close to that of an electrolyte material BZCY. In addition, co and Ni Co-doping can improve BaPrO to a certain extent 3 An upper limit of the B-bit doping amount of (c).
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is an XRD spectrum of a cathode powder of a perovskite type proton ceramic fuel cell single-phase cathode material and a preparation method thereof according to an embodiment of the invention;
FIG. 2 is a graph showing the thermal expansion of a bulk sample of a perovskite-type proton ceramic fuel cell single-phase cathode material and method of making same according to one embodiment of the invention;
FIG. 3 is an impedance spectrum at 700℃ for different cathode single cells of an embodiment of a perovskite type proton ceramic fuel cell single-phase cathode material and method of making the same according to the present invention;
FIG. 4 is a graph of current-voltage-power density at 700℃ for different cathode single cells of an embodiment of a perovskite-type proton ceramic fuel cell single-phase cathode material and method of making the same according to the invention;
FIG. 5 shows a single-phase cathode material for perovskite type proton ceramic fuel cell and a BaPr method for preparing the same according to an embodiment of the invention 0.8 Co 0.1 Ni 0.1 O 3 The single cell was at 600℃and 0.2A cm -2 A voltage curve of 120 hours of constant current discharge;
FIG. 6 shows a BaPr of a perovskite type proton ceramic fuel cell single-phase cathode material and a preparation method thereof according to an embodiment of the invention 0.8 Co 0.1 Ni 0.1 O 3 Microcosmic topography of the cell cross section.
Detailed Description
The technical scheme of the invention is further described below through the attached drawings and the embodiments.
Unless defined otherwise, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
Example 1
1. Preparation of cathode powder
(1) S1, respectively weighing Ba (NO) according to a stoichiometric ratio of 1:1 3 ) 2 、Pr(NO 3 ) 3 ·6H 2 O metal nitrate, according to metal ions: ethylenediamine tetraacetic acid: citric acid = 1:1:1.5 (molar ratio) weighing ethylenediamine tetraacetic acid and citric acid;
s2, pouring metal nitrate into a beaker, adding deionized water, stirring at 80 ℃ until the solution is clear, adding ethylenediamine tetraacetic acid, slowly dropwise adding ammonia water until the ethylenediamine tetraacetic acid is dissolved, adding citric acid and ammonia water, adjusting the pH value of the solution to 8, and keeping the solution stirring at 80 ℃ until gel is formed;
s3, placing the gel obtained in the step S2 into an oven, and drying at 280 ℃ for 5 hours until the gel dries to obtain a precursor;
s4, grinding the precursor in the step S3, then placing the ground precursor into a muffle furnace, and calcining the ground precursor for 5 hours at 1100 ℃ in an air atmosphere to obtain BaPrO 3 Cathode powder.
(2) S1, respectively weighing Ba (NO) according to a material stoichiometric ratio of 10:9:1 3 ) 2 、Pr(NO 3 ) 3 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O metal nitrate, according to metal ions: ethylenediamine tetraacetic acid: citric acid = 1:1:1.5 (molar ratio) weighing ethylenediamine tetraacetic acid and citric acid;
s2, pouring metal nitrate into a beaker, adding deionized water, stirring at 80 ℃ until the solution is clear, adding ethylenediamine tetraacetic acid, slowly dropwise adding ammonia water until the ethylenediamine tetraacetic acid is dissolved, adding citric acid and ammonia water, adjusting the pH value of the solution to 8, and keeping the solution stirring at 80 ℃ until gel is formed;
s3, placing the gel obtained in the step S2 into an oven, and drying at 280 ℃ for 5 hours until the gel dries to obtain a precursor;
s4, grinding the precursor in the step S3, then placing the ground precursor into a muffle furnace, and calcining the ground precursor for 5 hours at 1100 ℃ in an air atmosphere to obtain BaPr 0.9 Co 0.1 O 3 Cathode powder.
(3) S1, respectively weighing Ba (NO) according to a material stoichiometric ratio of 10:9:1 3 ) 2 、Pr(NO 3 ) 3 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O metal nitrate, according to metal ions: ethylenediamine tetraacetic acid: citric acid = 1:1:1.5 (molar ratio) weighing ethylenediamine tetraacetic acid and citric acid;
s2, pouring metal nitrate into a beaker, adding deionized water, stirring at 80 ℃ until the solution is clear, adding ethylenediamine tetraacetic acid, slowly dropwise adding ammonia water until the ethylenediamine tetraacetic acid is dissolved, adding citric acid and ammonia water, adjusting the pH value of the solution to 8, and keeping the solution stirring at 80 ℃ until gel is formed;
s3, placing the gel obtained in the step S2 into an oven, and drying at 280 ℃ for 5 hours until the gel dries to obtain a precursor;
s4, preceding step S3Grinding the precursor, putting into a muffle furnace, calcining at 1100 ℃ for 5 hours in an air atmosphere to obtain BaPr 0.9 Ni 0.1 O 3 Cathode powder.
(4) S1, respectively weighing Ba (NO) according to a material stoichiometric ratio of 10:8:1:1 3 ) 2 、Pr(NO 3 ) 3 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O metal nitrate, according to metal ions: ethylenediamine tetraacetic acid: citric acid = 1:1:1.5 (molar ratio) weighing ethylenediamine tetraacetic acid and citric acid;
s2, pouring metal nitrate into a beaker, adding deionized water, stirring at 80 ℃ until the solution is clear, adding ethylenediamine tetraacetic acid, slowly dropwise adding ammonia water until the ethylenediamine tetraacetic acid is dissolved, adding citric acid and ammonia water, adjusting the pH value of the solution to 8, and keeping the solution stirring at 80 ℃ until gel is formed;
s3, placing the gel obtained in the step S2 into an oven, and drying at 280 ℃ for 5 hours until the gel dries to obtain a precursor;
s4, grinding the precursor in the step S3, then placing the ground precursor into a muffle furnace, and calcining the ground precursor for 5 hours at 1100 ℃ in an air atmosphere to obtain BaPr 0.8 Co 0.1 Ni 0.1 O 3 Cathode powder.
(5) S1, respectively weighing Ba (NO) according to a material stoichiometric ratio of 5:4:1 3 ) 2 、Pr(NO 3 ) 3 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O metal nitrate, according to metal ions: ethylenediamine tetraacetic acid: citric acid = 1:1:1.5 (molar ratio) weighing ethylenediamine tetraacetic acid and citric acid;
s2, pouring metal nitrate into a beaker, adding deionized water, stirring at 80 ℃ until the solution is clear, adding ethylenediamine tetraacetic acid, slowly dropwise adding ammonia water until the ethylenediamine tetraacetic acid is dissolved, adding citric acid and ammonia water, adjusting the pH value of the solution to 8, and keeping the solution stirring at 80 ℃ until gel is formed;
s3, placing the gel obtained in the step S2 into an oven, and drying at 280 ℃ for 5 hours until the gel dries to obtain a precursor;
s4, grinding the precursor in the step S3, then placing the ground precursor into a muffle furnace, and calcining the ground precursor for 5 hours at 1100 ℃ in an air atmosphere to obtain BaPr 0.8 Co 0.2 O 3 Cathode powder.
(6) S1, respectively weighing Ba (NO) according to a material stoichiometric ratio of 5:4:1 3 ) 2 、Pr(NO 3 ) 3 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O metal nitrate, according to metal ions: ethylenediamine tetraacetic acid: citric acid = 1:1:1.5 (molar ratio) weighing ethylenediamine tetraacetic acid and citric acid;
s2, pouring metal nitrate into a beaker, adding deionized water, stirring at 80 ℃ until the solution is clear, adding ethylenediamine tetraacetic acid, slowly dropwise adding ammonia water until the ethylenediamine tetraacetic acid is dissolved, adding citric acid and ammonia water, adjusting the pH value of the solution to 8, and keeping the solution stirring at 80 ℃ until gel is formed;
s3, placing the gel obtained in the step S2 into an oven, and drying at 280 ℃ for 5 hours until the gel dries to obtain a precursor;
s4, grinding the precursor in the step S3, then placing the ground precursor into a muffle furnace, and calcining the ground precursor for 5 hours at 1100 ℃ in an air atmosphere to obtain BaPr 0.8 Ni 0.2 O 3 Cathode powder.
The XRD spectrum of the cathode powder prepared by the method is shown in figure 1, wherein BaPrO 3 、BaPr 0.9 Co 0.1 O 3 And BaPr 0.9 Ni 0.1 O 3 The powder sample is pure phase, no impurity exists, and when the doping amount is increased to 20mol percent, baPr 0.8 Co 0.2 O 3 And BaPr 0.8 Ni 0.2 O 3 The powder samples all have hetero-phase, and when the total doping amount is 20mol percent, co and Ni are Co-doped to prepare BaPr 0.8 Co 0.1 Ni 0.1 O 3 Is pure phase.
Example two
Conductivity and thermal expansion test
Placing part of cathode powder into square mold, maintaining pressure at 15Mpa for 2 min, demolding to obtain strip-shaped blank, and placing into muffle furnaceFiring at 1250℃for 6 hours gave the desired dense block. Characterization of the thermal expansion coefficient of the prepared strip sample using a thermal expansion instrument, wherein the test temperature ranges from room temperature to 800 ℃ and the temperature rising rate is 10 ℃ for min -1 . The results are shown in FIG. 2, wherein BaPrO 3 、BaPr 0.9 Co 0.1 O 3 、BaPr 0.9 Ni 0.1 O 3 、BaPr 0.8 Co 0.1 Ni 0.1 O 3 The average thermal expansion coefficients of the samples in the temperature range of 100-800 ℃ are 11.9X10 respectively -6 、12.7×10 -6 、11.7×10 -6 、12.9×10 -6 K -1 Are all in contact with the electrolyte BZCY (10.1X10) -6 K -1 ) Close.
Example III
Electrochemical performance test
(1) The preparation method of the single cell comprises the following steps:
1. firstly, weighing a certain amount of NiO-BaZr 0.1 Ce 0.7 Y 0.2 O 3 Powder and starch (starch mass is NiO-BaZr) 0.1 Ce 0.7 Y 0.2 O 3 15% of the powder mass) is placed in a ball milling tank, absolute ethyl alcohol is added, and the rotating speed is 200r min -1 Ball milling for 12 hours, followed by drying to remove absolute ethanol to obtain support powder.
2. Weighing 0.5g of support powder, placing the support powder into a circular mold, maintaining the pressure at 10Mpa for 1 min, demolding to obtain a support blank, and placing the support blank into a muffle furnace for presintering at 1000 ℃ for later use.
3. NiO-BaZr 0.1 Ce 0.7 Y 0.2 O 3 Adding the powder into absolute ethanol, adding polyethylene glycol, polyvinyl butyral, triethanolamine and dimethyl phthalate, and rotating at 250r min -1 Ball milling for 12 hours to obtain anode suspension. BZCY electrolyte suspensions were prepared in the same manner.
4. And taking anode suspension liquid by using a rubber head dropper, dripping the anode suspension liquid on the surface of a support body, drying the support body at room temperature, then putting the support body into a muffle furnace, slowly heating the support body to 500 ℃ to remove organic matters in an anode layer, dripping electrolyte suspension liquid on the surface of the anode layer, drying the support body, covering BZCY powder, putting the support body into the muffle furnace, heating the support body to 1300 ℃, and sintering the support body for 6 hours to obtain the half-cell.
5. The prepared cathode powder is rotated at the speed of 250r min -1 After ball milling for 12 hours, the mixture is mixed with a binder (ethyl cellulose and turpentine alcohol mixture, wherein the ethyl cellulose accounts for 4 wt%) according to the mass ratio of 1:1, fully mixing to obtain cathode slurry.
6. The cathode slurry was uniformly coated on the prepared half cell by a knife coating method, and fired at 1000 ℃ for 2 hours to obtain a single cell. The electrolyte thickness is about 10 microns, the cathode thickness is about 26 microns, and the effective area of the cathode is 0.196cm -2 。
(2) Impedance spectroscopy test
Silver paste is coated on the surface of the cathode to serve as a current collecting layer, and then the battery is sealed on the ceramic tube by using conductive silver paste and connected with a circuit. Introducing 20ml of the mixture into a ceramic tube for min -1 Wetting H 2 (3%H 2 O) as a fuel gas, and the cathode is exposed to air. Impedance test is carried out on the battery in an open circuit state, the disturbance voltage is 10mV, and the frequency range is 10 6 About 0.1Hz, and the test temperature is 700 ℃. The results are shown in FIG. 3, baPrO 3 Ohmic and polarization impedances of the single cells were 0.55 Ω cm, respectively 2 And 0.29 Ω cm 2 ,BaPr 0.9 Co 0.1 O 3 Ohmic and polarization impedances of the single cells were 0.30 Ω cm, respectively 2 And 0.11 Ω cm 2 ,BaPr 0.9 Ni 0.1 O 3 Ohmic and polarization impedances of the single cells were 0.26 Ω cm, respectively 2 And 0.20 Ω cm 2 ,BaPr 0.8 Co 0.1 Ni 0.1 O 3 Ohmic and polarization impedances of the single cells were 0.17 Ω cm, respectively 2 And 0.06 Ω cm 2 。
(3) Battery power density testing
And applying a continuously-changing linear voltage to the battery, measuring an output current value, and calculating to obtain the power density of the battery. The scanning voltage ranges from-0.8V to 0V, and the scanning speed is 20mV s -1 The test temperature was 700 ℃. The cathode was exposed to static air during the test, and the anode side was vented for 20mL min -1 Is (3%H) 2 O). The results are shown in the graph4, baPrO 3 、BaPr 0.9 Co 0.1 O 3 、BaPr 0.9 Ni 0.1 O 3 Peak power densities of the single cells were 0.30, 0.56, and 0.44Wcm, respectively -2 ,BaPr 0.8 Co 0.1 Ni 0.1 O 3 The peak power density of the single cell was 0.85Wcm -2 Far higher than the other three single cells.
(4) Stability test
To investigate the stability of BPCN as a cathode for PCFC, a constant current discharge test was performed on BPCN cells at 600 ℃. The test temperature is 600 ℃, the cathode is exposed to static air during the test, and the anode side is introduced with 20mL for min -1 Is (3%H) 2 O) discharge current density of 0.2A cm -2 The results are shown in FIG. 5, which shows BaPr 0.8 Co 0.1 Ni 0.1 O 3 The cell cross-sectional microtopography is shown in fig. 6.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting it, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that: the technical scheme of the invention can be modified or replaced by the same, and the modified technical scheme cannot deviate from the spirit and scope of the technical scheme of the invention.
Claims (6)
1. A perovskite type proton ceramic fuel cell single-phase cathode material is characterized in that: molecular formula is BaPr 1-x- y Co x Ni y O 3 ,0<x≤0.2,0<y≤0.2。
2. A method for preparing the perovskite type proton ceramic fuel cell single-phase cathode material as claimed in claim 1, comprising the following steps:
s1, respectively weighing metal nitrates of Ba, pr, co and Ni according to the stoichiometric ratio of the materials, and weighing ethylenediamine tetraacetic acid and citric acid;
s2, pouring metal nitrate into a beaker, adding deionized water, stirring at 80 ℃ until the solution is clear, adding ethylenediamine tetraacetic acid, slowly dropwise adding ammonia water until the ethylenediamine tetraacetic acid is dissolved, adding citric acid and ammonia water, regulating the pH value of the solution, and stirring until gel is formed;
s3, placing the gel obtained in the step S2 into an oven, and drying at 280 ℃ for 5 hours until the gel dries to obtain a precursor;
and S4, grinding the precursor in the step S3, and then placing the ground precursor into a muffle furnace to calcine the ground precursor in an air atmosphere to obtain cathode powder.
3. The method for preparing the perovskite type proton ceramic fuel cell single-phase cathode material as claimed in claim 2, wherein the method comprises the following steps: in the S1 step, the metal nitrates of Ba, pr, co and Ni are Ba (NO 3 ) 2 、Pr(NO 3 ) 3 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O and Ni (NO) 3 ) 2 ·6H 2 O。
4. The method for preparing the perovskite type proton ceramic fuel cell single-phase cathode material as claimed in claim 2, wherein the method comprises the following steps: in the step S1, according to metal ions: ethylenediamine tetraacetic acid: molar ratio of citric acid = 1:1:1.5 ethylenediamine tetraacetic acid and citric acid were weighed.
5. The method for preparing the perovskite type proton ceramic fuel cell single-phase cathode material as claimed in claim 2, wherein the method comprises the following steps: in step S2, the pH value of the solution is adjusted to 8, and the stirring temperature is 80 ℃.
6. The method for preparing the perovskite type proton ceramic fuel cell single-phase cathode material as claimed in claim 2, wherein the method comprises the following steps: in step S4, the calcination temperature was 1100 ℃.
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