CN114300722A - Oxide ceramic electrolyte composite material and preparation method and application thereof - Google Patents
Oxide ceramic electrolyte composite material and preparation method and application thereof Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 229910052574 oxide ceramic Inorganic materials 0.000 title claims abstract description 49
- 239000011224 oxide ceramic Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000010405 anode material Substances 0.000 claims abstract description 15
- 239000000446 fuel Substances 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- 238000001035 drying Methods 0.000 claims description 40
- 238000001354 calcination Methods 0.000 claims description 35
- 239000008139 complexing agent Substances 0.000 claims description 23
- 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 description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 159000000003 magnesium salts Chemical class 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 238000000137 annealing Methods 0.000 claims description 16
- 150000002751 molybdenum Chemical class 0.000 claims description 16
- 159000000008 strontium salts Chemical class 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 13
- 239000012670 alkaline solution Substances 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 11
- 230000000536 complexating effect Effects 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052799 carbon Inorganic materials 0.000 abstract description 15
- -1 oxygen ion Chemical class 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 3
- 238000009825 accumulation Methods 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002737 fuel gas Substances 0.000 abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 29
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical group [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 26
- 239000000843 powder Substances 0.000 description 22
- 229910052712 strontium Inorganic materials 0.000 description 18
- 210000004027 cell Anatomy 0.000 description 17
- 229960001484 edetic acid Drugs 0.000 description 17
- 238000000227 grinding Methods 0.000 description 14
- 239000012266 salt solution Substances 0.000 description 14
- 239000000523 sample Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 150000004696 coordination complex Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 4
- 239000011609 ammonium molybdate Substances 0.000 description 4
- 229940010552 ammonium molybdate Drugs 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 3
- 229910002141 La0.6Sr0.4CoO3-δ Inorganic materials 0.000 description 3
- 229910002201 La0.8Sr0.2Ga0.83Mg0.17O3−δ Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical group [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910002412 SrMoO4 Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910002119 nickel–yttria stabilized zirconia Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
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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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- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of solid oxide fuel cells, and particularly relates to an oxide ceramic electrolyte composite material and a preparation method and application thereof. The oxide ceramic electrolyte composite material provided by the invention adopts double perovskite anode material Sr2MgMoO6The perovskite Structure of (SMMO) can form oxygen vacancy, so that the (SMMO) perovskite structure has good oxygen ion transmission performance, Mo atomic sites are easy to form main catalytic reaction centers, and the (SMMO) perovskite structure has higher sulfur resistance, carbon deposition resistance and high temperature stability, and can reduce the carbon accumulation and sulfur accumulation of Ni in hydrocarbon fuel gas due to the generation of carbonThe catalyst activity is lost due to toxicity, so that the catalyst activity is improved; mo ions in the SMMO structure are in a mixed valence state and have good electronic conductivity, so that the conductivity of the oxide ceramic electrolyte composite material is improved.
Description
Technical Field
The invention belongs to the technical field of solid oxide fuel cells, and particularly relates to an oxide ceramic electrolyte composite material and a preparation method and application thereof.
Background
A Solid Oxide Fuel Cell (SOFC) is an electrochemical reactor which can directly convert chemical energy of fuels such as hydrogen, hydrocarbon and the like into electric energy, has high energy conversion efficiency, has the advantages of small pollution, flexible fuel and the like, and is a novel power generation device with great application potential. The traditional SOFC has the working temperature as high as 1000 ℃, which has extremely high requirements on cell materials and accessory equipment thereof, and causes the problems of poor compatibility among cell components and high cost of cell construction, operation and maintenance. Reducing the operating temperature of the SOFC will facilitate improved cell component material suitability, longer cell life, and lower operating costs. Therefore, the medium-low temperature technology (500-800 ℃) becomes a hot spot of modern SOFC research.
In current medium and low temperature technologies, the anode functional component still uses traditional metal-ceramic composite material, such as Ni-YSZ (Y)2xZr1-2xO2-x) Or Ni-SDC (Ce)1-xSmxO2-δ) The catalytic component Ni microcrystal particles are obtained by reducing NiO through fuel gas, and the ceramic component in the metal-ceramic composite material is porous electrolyte. In the metal-electrolyte ceramic composite anode material, the electrolyte component has the main function of dispersing the catalytic component, and the three-phase reaction interface of fuel gas-electrode-electrolyte can be increased due to the good oxygen ion transmission performance, so that the anode reaction speed is increased. However, the introduction of ceramic electrolytes also brings significant drawbacks and disadvantages. The introduction of ceramic electrolyte is not to a certain extentThe catalytic performance of part of Ni catalyst is inevitably sacrificed, because compared with metal Ni, the ceramic component has extremely low electronic conductivity, which is not beneficial to collecting anode current, thus being not beneficial to reducing ohmic resistance of the electrode, and further leading to lower catalytic activity and conductivity of the metal-ceramic composite anode material.
Disclosure of Invention
In view of the above, the present invention provides an oxide ceramic electrolyte composite material, and a preparation method and an application thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides an oxide ceramic electrolyte composite material which comprises blended NiO and Sr2MgMoO6Said Sr2MgMoO6The mass of the NiO is (0, 80%) of the mass of the oxide ceramic electrolyte composite material](ii) a Said Sr2MgMoO6Is a monoclinic structure, the Sr2MgMoO6Space group of (2) is P21N, the Sr2MgMoO6Wherein Mo includes Mo6+And Mo5+。
The invention also provides a preparation method of the oxide ceramic electrolyte composite material in the technical scheme, which comprises the following steps:
mixing a magnesium salt, a strontium salt, a molybdenum salt, a complexing agent and an alkaline solution, and sequentially carrying out a complexing reaction and drying to obtain dry gel;
the xerogel is sequentially calcined and annealed to obtain Sr2MgMoO6；
Subjecting said Sr to2MgMoO6And mixing with NiO, and performing ball milling to obtain the oxide ceramic electrolyte composite material.
Preferably, the molar ratio of the magnesium salt, the strontium salt and the molybdenum salt is 1: 2: 1.
Preferably, the complexing agent comprises citric acid and ethylenediaminetetraacetic acid; the mol ratio of the complexing agent to the total metal ions in the magnesium salt, the strontium salt and the molybdenum salt is 3: 1; the mol ratio of citric acid to ethylenediamine tetraacetic acid in the complexing agent is 2: 1.
Preferably, the calcining process comprises a first calcining and a second calcining which are sequentially carried out; the temperature of the first calcination is 400-450 ℃; the first calcining time is 5-10 h; the temperature of the second calcination is 600-800 ℃; and the second calcining time is 8-10 h.
Preferably, the annealing temperature is 1100-1200 ℃; the annealing time is 20-30 h.
Preferably, the annealing is performed in a mixed atmosphere of argon and hydrogen; the volume ratio of the argon to the hydrogen is (90-95) to (5-10).
Preferably, the rotation speed of the ball milling is 200-300 r/min.
Preferably, the ball milling time is 2-3 h.
The invention also provides the application of the oxide ceramic electrolyte composite material in the technical scheme in the anode material of the solid oxide fuel cell.
The invention provides an oxide ceramic electrolyte composite material which comprises blended NiO and Sr2MgMoO6Said Sr2MgMoO6The mass of the NiO is (0, 80%) of the mass of the oxide ceramic electrolyte composite material](ii) a Said Sr2MgMoO6Is a monoclinic structure, the Sr2MgMoO6Space group of (2) is P21N, the Sr2MgMoO6Wherein Mo includes Mo6+And Mo5+. The oxide ceramic electrolyte composite material provided by the invention adopts double perovskite anode material Sr2MgMoO6(SMMO) is used as a ceramic component, the perovskite structure of the SMMO can form oxygen vacancy, so that the SMMO has good oxygen ion transmission performance, has higher sulfur resistance, carbon deposition resistance and high-temperature stability, and can reduce the problem that Ni loses catalytic activity due to carbon accumulation and sulfur poisoning in hydrocarbon fuel gas, thereby improving the oxideCatalytic activity of the ceramic electrolyte composite; in addition, in the SMMO structure, Mo element has good valence-changing capability, and Mo which can be formed6+/Mo5+Redox couple, so that Mo atom site is easy to form main catalytic reaction center, and Mo ion with 4d electronic arrangement is mixed valence state (Mo6+And Mo5+) Thereby the material has good electronic conductivity, and the conductivity of the oxide ceramic electrolyte composite material is improved. In addition, compared with single-phase anode material Sr2MgMoO6The NiO in the oxide ceramic electrolyte composite material provided by the invention can be reduced into the simple substance Ni, so that the oxide ceramic electrolyte composite material has higher conductivity and lower interface impedance. The results of the examples show that the output of an electrolyte supported single cell can reach 640mW/cm at 800 ℃ when hydrogen is used as fuel and an oxide ceramic electrolyte composite material with x being 40 wt.% is used as an anode2。
The preparation method of the oxide ceramic electrolyte composite material provided by the invention has low requirements on synthesis equipment, is simple to operate, has no special requirements on a battery sintering preparation process, and the synthesized material has a stable structure and is environment-friendly.
Drawings
FIG. 1 shows NiO-40 wt.% Sr as a product in example 1 of this invention2MgMoO6SEM picture of (1);
FIG. 2 shows NiO-40 wt.% Sr as a product in example 1 of this invention2MgMoO6An electrochemical impedance map of (a);
FIG. 3 shows NiO-40 wt.% Sr as a product in example 1 of this invention2MgMoO6The working voltage and the power density of the single battery are changed along with the current density under different temperatures;
FIG. 4 shows NiO-20 wt.% Sr as a product in example 2 of this invention2MgMoO6SEM picture of (1);
FIG. 5 shows NiO-20 wt.% Sr as a product in example 2 of this invention2MgMoO6An electrochemical impedance map of (a);
FIG. 6 shows NiO-20 wt.% Sr as a product in example 2 of this invention2MgMoO6Are different from each otherA trend graph of the working voltage and the power density along with the current density change under the temperature;
FIG. 7 shows Sr, a comparative example 1 according to the present invention2MgMoO6XRD pattern of (a);
FIG. 8 shows Sr, a comparative example 1 of the present invention2MgMoO6SEM picture of (1);
FIG. 9 shows Sr, a comparative example 1 of the present invention2MgMoO6An electrochemical impedance map of (a);
FIG. 10 shows Sr, a comparative example 1 of the present invention2MgMoO6The working voltage and the power density of the single battery are changed along with the current density under different temperatures.
Detailed Description
The invention provides an oxide ceramic electrolyte composite material which comprises blended NiO and Sr2MgMoO6Said Sr2MgMoO6The mass of the NiO is (0, 80%) of the mass of the oxide ceramic electrolyte composite material](ii) a Said Sr2MgMoO6Is a monoclinic structure, the Sr2MgMoO6Space group of (2) is P21N, the Sr2MgMoO6Wherein Mo includes Mo6+And Mo5+。
The oxide ceramic electrolyte composite material provided by the invention comprises NiO, wherein the mass of the NiO is (0, 80%) and preferably [ 60%, 80%) of the mass of the oxide ceramic electrolyte composite material, and the NiO is preferably nano oxide particles.
The oxide ceramic electrolyte composite material provided by the invention comprises Sr2MgMoO6Said Sr2MgMoO6Is [ 20%, 100%) of the mass of the oxide ceramic electrolyte composite material, preferably [ 20%, 40%]Said Sr2MgMoO6Is a monoclinic structure, the Sr2MgMoO6Space group of (2) is P21N, the Sr2MgMoO6Wherein Mo includes Mo6+And Mo5+。
The invention also provides a preparation method of the oxide ceramic electrolyte composite material in the technical scheme, which comprises the following steps:
mixing a magnesium salt, a strontium salt, a molybdenum salt, a complexing agent and an alkaline solution, and sequentially carrying out a complexing reaction and drying to obtain dry gel;
the xerogel is sequentially calcined and annealed to obtain Sr2MgMoO6；
Subjecting said Sr to2MgMoO6And mixing with NiO, and performing ball milling to obtain the oxide ceramic electrolyte composite material.
Unless otherwise specified, the present invention does not require any particular source of the raw materials used, and commercially available products known to those skilled in the art may be used.
The invention mixes the magnesium salt, the strontium salt, the molybdenum salt, the complexing agent and the alkaline solution, and carries out complexing reaction and drying in sequence to obtain the xerogel.
In the present invention, the magnesium salt is preferably magnesium nitrate; the magnesium salt is preferably used in the form of a solution, the solution of the magnesium salt is preferably a magnesium nitrate solution, and the preparation method of the magnesium nitrate solution preferably comprises the following steps: and (2) putting the light magnesium oxide powder into a high-temperature furnace, calcining for 2-4 h at 900-950 ℃, then adding concentrated nitric acid after the calcined light magnesium oxide powder is cooled to below 120 ℃, and completely dissolving the light magnesium oxide powder to obtain a magnesium nitrate solution.
In the present invention, the strontium salt is preferably strontium nitrate; the molybdenum salt is preferably ammonium molybdate; the preferred molar ratio of the magnesium salt, the strontium salt and the molybdenum salt is 1: 2: 1. The process of mixing the magnesium salt solution, the strontium salt and the molybdenum salt is not particularly limited in the invention, and the strontium salt and the molybdenum salt can be completely dissolved by adopting the mixing process well known in the field.
In the present invention, the complexing agent preferably includes citric acid and ethylenediaminetetraacetic acid; the mol ratio of the complexing agent to the total metal ions in the magnesium salt, the strontium salt and the molybdenum salt is preferably 3: 1; the mol ratio of citric acid to ethylenediamine tetraacetic acid in the complexing agent is preferably 2: 1; the alkaline solution is preferably ammonia.
In the invention, the process of mixing the magnesium salt, the strontium salt, the molybdenum salt, the complexing agent and the alkaline solution is preferably to mix the magnesium salt solution, the strontium salt and the molybdenum salt to obtain a mixed salt solution, and then mix the mixed salt solution, the complexing agent and the alkaline solution; preferably, the mixed salt solution, the complexing agent and the alkaline solution are mixed firstly, then the alkaline solution is added for stirring until the ethylenediamine tetraacetic acid is completely dissolved to obtain a clear solution, and then the alkaline solution is added to adjust the pH value of the clear solution to 8-9 to obtain a light yellow metal complexing solution.
The invention mixes the magnesium salt, strontium salt, molybdenum salt, complexing agent and alkaline solution to obtain the material, and carries out complexing reaction and drying in sequence to obtain xerogel.
The process of the complexing reaction is not particularly limited in the present invention, and a complexing reaction process well known in the art may be used. A metal ion complexation reaction occurs during the complexation reaction.
In the present invention, the drying process preferably includes a first drying and a second drying which are sequentially performed; the first drying temperature is preferably 80-100 ℃, and more preferably 90-100 ℃; the second drying temperature is preferably 150-180 ℃, and more preferably 150-160 ℃; the drying apparatus is preferably an oven. The method comprises the steps of drying and evaporating most of moisture in the metal complex solution at low temperature to obtain viscous gel, and then drying at high temperature until the moisture in the viscous gel is completely dried to obtain dry gel. The first drying time is not particularly limited in the present invention, and the drying time known in the art may be adopted until the metal complex solution becomes a viscous gel; the time for the second drying is not particularly limited in the present invention, and drying time known in the art is used until the moisture in the viscous gel is completely dried to obtain a xerogel.
After obtaining the dry gel, the invention sequentially calcines and anneals the dry gel to obtain Sr2MgMoO6。
In the present invention, the calcination process preferably includes a first calcination and a second calcination performed in this order; the temperature of the first calcination is preferably 400-450 ℃, and more preferably 410-450 ℃; the first calcination time is preferably 5-10 h, and more preferably 5-8 h; the second calcining temperature is preferably 600-800 ℃, and more preferably 700-800 ℃; the second calcination time is preferably 8-10 h, and more preferably 8-9 h. The xerogel is calcined in the first calcination stage to obtain a carbon ash-shaped oxide precursor, and then the carbon ash-shaped oxide precursor is ground into powder and then is subjected to second calcination to obtain white powder. The process of the grinding is not particularly limited in the present invention, and a grinding process well known in the art may be used. In the present invention, the calcination apparatus is preferably a muffle furnace.
After the calcination is completed, the invention preferably grinds and dries the calcined product to obtain fine powder; the grinding process is not particularly limited in the present invention, and the white powder may be sufficiently ground to a fine powder by a grinding process well known in the art. The drying process is not particularly limited in the present invention, and a drying process well known in the art may be used.
After obtaining the fine powder, the present invention preferably molds the fine powder to obtain a stamper. In the present invention, the mode of the casting mold is preferably axial compression; the pressure of the axial pressure is preferably 100 MPa.
After obtaining the matrix, the invention anneals the matrix to obtain Sr2MgMoO6。
In the invention, the annealing temperature is preferably 1100-1200 ℃, and more preferably 1100-1150 ℃; the annealing time is preferably 20-30 h, and more preferably 20-25 h; the annealing is preferably carried out in a mixed atmosphere of argon and hydrogen; the volume ratio of the argon to the hydrogen is preferably (90-95) to (5-10), and more preferably 95: 5; the annealing apparatus is preferably a tube furnace.
The present invention preferably repeats the "grinding, drying, molding and annealing" more than 2 times until the Sr is reached2MgMoO6The phase state of the compound is pure.
To obtain Sr2MgMoO6Then, the present invention converts the Sr2MgMoO6Mixing with NiO, ball milling to obtain oxideA ceramic electrolyte composite.
In the present invention, said Sr2MgMoO6Is preferably Sr2MgMoO6And NiO, 20-100%, and preferably 20-40%; the rotation speed of the ball milling is preferably 200-300 r/min, and more preferably 250-300 r/min; the time for ball milling is preferably 2-3 h, and more preferably 3 h.
The invention also provides the application of the oxide ceramic electrolyte composite material in the technical scheme in the anode material of the solid oxide fuel cell.
The application mode of the oxide ceramic electrolyte composite material in the solid oxide fuel cell is not particularly limited, and the application method well known in the field can be adopted.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
Putting the light magnesium oxide powder into a high-temperature furnace, calcining for 2h at 950 ℃, pouring into a beaker after cooling to 120 ℃, and adding concentrated nitric acid to completely dissolve the light magnesium oxide powder to obtain a magnesium nitrate solution; then adding Sr (NO) into the magnesium nitrate solution3)2And H24Mo7N6O24·4H2Making magnesium nitrate, Sr (NO) by O (ammonium molybdate)3)2And H24Mo7N6O24·4H2The molar ratio of metal salt ions in the O is 1: 2: 1, and a mixed salt solution is obtained by stirring and dissolving; adding citric acid (CIT) and Ethylene Diamine Tetraacetic Acid (EDTA) into the mixed salt solution as complexing agents, wherein the molar ratio of the complexing agents to total metal ions in the mixed salt solution is 3: 1, the molar ratio of the citric acid to the ethylene diamine tetraacetic acid is 2: 1, then adding strong ammonia water, stirring until all EDTA is dissolved to obtain a clear solution, and continuously adding the strong ammonia water to adjust the pH value of the clear solution to 8 to obtain a light yellow metal complexing solution; drying the metal complex solution in a 100 ℃ oven to evaporate most of water to obtain viscous gel, heating to 150 ℃ for continuous drying, and drying the viscous gelThe water in the gel is thoroughly dried to obtain dry gel; calcining the dried gel in a muffle furnace at 450 ℃ for 5h to obtain a carbon ash-shaped product, grinding and drying the carbon ash-shaped product, and further calcining the carbon ash-shaped product in the muffle furnace at 800 ℃ for 8h to obtain white powder; fully grinding and drying the white powder, then molding into a sheet under the axial pressure of 100MPa, putting the obtained sheet into a tube furnace with the mixed atmosphere of argon and hydrogen with the volume ratio of 95: 5, annealing for 24 hours at 1100 ℃, and repeating the steps of grinding, drying, molding and annealing for 3 times until Sr is reached2MgMoO6The phase state tends to be pure, and finally Sr is added2MgMoO6Mixing the NiO and NiO according to the mass ratio of 40: 60, and performing ball milling for 3h at 300r/min to obtain NiO-40 wt.% Sr2MgMoO6An oxide ceramic electrolyte composite.
Example 2
Putting the light magnesium oxide powder into a high-temperature furnace, calcining for 2h at 950 ℃, pouring into a beaker after cooling to 120 ℃, and adding concentrated nitric acid to completely dissolve the light magnesium oxide powder to obtain a magnesium nitrate solution; then adding Sr (NO) into the magnesium nitrate solution3)2And H24Mo7N6O24·4H2Making magnesium nitrate, Sr (NO) by O (ammonium molybdate)3)2And H24Mo7N6O24·4H2The molar ratio of metal salt ions in the O is 1: 2: 1, and a mixed salt solution is obtained by stirring and dissolving; adding citric acid (CIT) and Ethylene Diamine Tetraacetic Acid (EDTA) into the mixed salt solution as complexing agents, wherein the molar ratio of the complexing agents to total metal ions in the mixed salt solution is 3: 1, the molar ratio of the citric acid to the ethylene diamine tetraacetic acid is 2: 1, then adding strong ammonia water, stirring until all EDTA is dissolved to obtain a clear solution, and continuously adding the strong ammonia water to adjust the pH value of the clear solution to 8 to obtain a light yellow metal complexing solution; drying the metal complex solution in a drying oven at 100 ℃ to evaporate most of water to obtain viscous gel, heating to 150 ℃ for continuous drying, and completely drying the water in the viscous gel to obtain dry gel; calcining the dried gel in a muffle furnace at 450 ℃ for 5 hours to obtain a carbon ash-shaped product, grinding and drying the carbon ash-shaped product, and then putting the carbon ash-shaped product in the muffle furnace at 800 DEG CFurther calcining for 8h to obtain white powder; fully grinding and drying the white powder, then molding into a sheet under the axial pressure of 100MPa, putting the obtained sheet into a tube furnace with the mixed atmosphere of argon and hydrogen with the volume ratio of 95: 5, annealing for 24 hours at 1100 ℃, and repeating the steps of grinding, drying, molding and annealing for 3 times until Sr is reached2MgMoO6The phase state tends to be pure, and finally Sr is added2MgMoO6Mixing NiO with NiO according to the mass ratio of 20: 80, and performing ball milling for 3h at 300r/min to obtain NiO-20 wt.% Sr2MgMoO6An oxide ceramic electrolyte composite.
Comparative example 1
Putting the light magnesium oxide powder into a high-temperature furnace, calcining for 2h at 950 ℃, pouring into a beaker after cooling to 120 ℃, and adding concentrated nitric acid to completely dissolve the light magnesium oxide powder to obtain a magnesium nitrate solution; then adding Sr (NO) into the magnesium nitrate solution3)2And H24Mo7N6O24·4H2Making magnesium nitrate, Sr (NO) by O (ammonium molybdate)3)2And H24Mo7N6O24·4H2The molar ratio of metal salt ions in the O is 1: 2: 1, and a mixed salt solution is obtained by stirring and dissolving; adding citric acid (CIT) and Ethylene Diamine Tetraacetic Acid (EDTA) into the mixed salt solution as complexing agents, wherein the molar ratio of the complexing agents to total metal ions in the mixed salt solution is 3: 1, the molar ratio of the citric acid to the ethylene diamine tetraacetic acid is 2: 1, then adding strong ammonia water, stirring until all EDTA is dissolved to obtain a clear solution, and continuously adding the strong ammonia water to adjust the pH value of the clear solution to 8 to obtain a light yellow metal complexing solution; drying the metal complex solution in a drying oven at 100 ℃ to evaporate most of water to obtain viscous gel, heating to 150 ℃ for continuous drying, and completely drying the water in the viscous gel to obtain dry gel; calcining the dried gel in a muffle furnace at 450 ℃ for 5h to obtain a carbon ash-shaped product, grinding and drying the carbon ash-shaped product, and further calcining the carbon ash-shaped product in the muffle furnace at 800 ℃ for 8h to obtain white powder; grinding white powder, drying, molding into tablet under 100MPa, and mixing with argon and hydrogen at volume ratio of 95: 5Annealing at 1100 deg.C for 24h in an atmosphere tube furnace, and repeating the "grinding, drying, casting and annealing" 3 times until Sr2MgMoO6The phase state tends to be pure to obtain Sr2MgMoO6An anode material.
And (3) performance testing:
(1) NiO-40 wt.% Sr oxide ceramic electrolyte composite prepared in example 12MgMoO6SEM observation was carried out, and the results are shown in FIG. 1.
As can be seen from FIG. 1, the oxide ceramic electrolyte composite NiO-40 wt.% Sr prepared in example 12MgMoO6The particles are relatively large, NiO is nano-particles, Sr2MgMoO6Substantially encapsulated by NiO nanoparticles.
(2) NiO-40 wt.% Sr in symmetric cells for the oxide ceramic electrolyte composite prepared in example 12MgMoO6Electrochemical impedance spectroscopy measurements of the interface between the sample anode material and the electrolyte are shown in FIG. 2, in which (a) is a Nyquist plot and (b) is a Bode plot.
As can be seen from FIG. 2, the oxide ceramic electrolyte composite NiO-40 wt.% Sr prepared in example 12MgMoO6The interfacial resistance of the sample anode material to the electrolyte was about 0.26 Ω cm2。
(3) NiO-40 wt.% Sr oxide ceramic electrolyte composite prepared in example 12MgMoO6The sample material is anode, La0.6Sr0.4CoO3-δIs a cathode, La0.8Sr0.2Ga0.83Mg0.17O3-δThe operating voltage and power density of the single cell (300. + -.10 μm) as the electrolyte were measured, and the results are shown in FIG. 3.
As can be seen from FIG. 3, the oxide ceramic electrolyte composite NiO-40 wt.% Sr prepared in example 12MgMoO6The highest output power of a single cell taking the sample material as the anode is about 640mW/cm at 800 DEG C2。
(4) NiO-20 wt.% Sr of the oxide ceramic electrolyte composite prepared in example 22MgMoO6SEM observation was conducted, and the results are shown in FIG. 4.
As can be seen from FIG. 4, the oxide ceramic electrolyte composite NiO-20 wt.% Sr prepared in example 22MgMoO6The particles are relatively large, NiO is nano-particles, Sr2MgMoO6Substantially encapsulated by NiO nanoparticles.
(5) NiO-20 wt.% Sr in symmetric cells for the oxide ceramic electrolyte composite prepared in example 22MgMoO6Electrochemical impedance spectroscopy measurements of the interface of the sample anode material and the electrolyte are performed, and the results are shown in fig. 5, in which (a) is a Nyquist diagram and (b) is a Bode diagram.
As can be seen from FIG. 5, the oxide ceramic electrolyte composite NiO-20 wt.% Sr prepared in example 22MgMoO6The interfacial resistance of the sample anode material to the electrolyte was about 1.25. omega. cm2。
(6) NiO-20 wt.% Sr oxide ceramic electrolyte composite prepared as in example 22MgMoO6Is an anode, La0.6Sr0.4CoO3-δIs a cathode, La0.8Sr0.2Ga0.83Mg0.17O3-δThe operating voltage and power density of the single cell (300. + -.10 μm) as the electrolyte were measured, and the results are shown in FIG. 6.
As can be seen from FIG. 6, the oxide ceramic electrolyte composite NiO-20 wt.% Sr prepared in example 22MgMoO6The highest output power of a single cell as an anode is about 410mW/cm at 800 DEG C2。
(7) Sr prepared in comparative example 12MgMoO6The sample was annealed twice at 1100 c for 24h and once at 1200 c for 24h and subjected to X-ray diffraction (XRD) analysis, the results of which are shown in fig. 7.
As can be seen from FIG. 7, Sr was obtained in comparative example 12MgMoO6The sample has high purity and only trace SrMoO4Impurities.
(8) Sr produced in comparative example 12MgMoO6The appearance of the sample was observed by SEM, and the results are shown in fig. 8.
As can be seen from FIG. 8, Sr was obtained in comparative example 12MgMoO6The particles of the sample are relatively large, on the order of 1 μm.
(9) Sr prepared in comparative example 1 in symmetrical cell2MgMoO6Electrochemical impedance spectroscopy measurements of the interface between the sample anode material and the electrolyte are performed, and the results are shown in fig. 9, in which (a) is a Nyquist diagram and (b) is a Bode diagram.
As can be seen from FIG. 9, Sr was obtained in comparative example 12MgMoO6The interfacial resistance of the sample anode material to the electrolyte was about 1.2. omega. cm2。
(10) For Sr prepared in comparative example 12MgMoO6The sample is an anode, La0.6Sr0.4CoO3-δIs a cathode, La0.8Sr0.2Ga0.83Mg0.17O3-δThe operating voltage and power density of the single cell (300. + -.10 μm) as an electrolyte were measured, and the results are shown in FIG. 10.
As can be seen from FIG. 10, Sr was obtained in the preparation of comparative example 12MgMoO6The highest output power of a single cell taking the sample as the anode is about 420mW/cm at 800 DEG C2。
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (10)
1. An oxide ceramic electrolyte composite material is characterized by comprising blended NiO and Sr2MgMoO6Said Sr2MgMoO6The mass of the NiO is (0, 80%) of the mass of the oxide ceramic electrolyte composite material](ii) a Said Sr2MgMoO6Is a monoclinic structure, the Sr2MgMoO6Space group of (2) is P21N, the Sr2MgMoO6Wherein Mo includes Mo6+And Mo5+。
2. A method for preparing the oxide ceramic electrolyte composite material according to claim 1, comprising the steps of:
mixing a magnesium salt, a strontium salt, a molybdenum salt, a complexing agent and an alkaline solution, and sequentially carrying out a complexing reaction and drying to obtain dry gel;
the xerogel is sequentially calcined and annealed to obtain Sr2MgMoO6；
Subjecting said Sr to2MgMoO6And mixing with NiO, and performing ball milling to obtain the oxide ceramic electrolyte composite material.
3. The method according to claim 2, wherein the molar ratio of the magnesium salt, the strontium salt and the molybdenum salt is 1: 2: 1.
4. The method of claim 2, wherein the complexing agent comprises citric acid and ethylenediaminetetraacetic acid; the mol ratio of the complexing agent to the total metal ions in the magnesium salt, the strontium salt and the molybdenum salt is 3: 1; the mol ratio of citric acid to ethylenediamine tetraacetic acid in the complexing agent is 2: 1.
5. The method according to claim 2, wherein the calcination comprises a first calcination and a second calcination performed in this order; the temperature of the first calcination is 400-450 ℃; the first calcining time is 5-10 h; the temperature of the second calcination is 600-800 ℃; and the second calcining time is 8-10 h.
6. The preparation method according to claim 2, wherein the annealing temperature is 1100-1200 ℃; the annealing time is 20-30 h.
7. The method of claim 6, wherein the annealing is performed in a mixed atmosphere of argon and hydrogen; the volume ratio of the argon to the hydrogen is (90-95) to (5-10).
8. The preparation method of claim 2, wherein the rotation speed of the ball mill is 200-300 r/min.
9. The preparation method of claim 2, wherein the ball milling time is 2-3 h.
10. Use of the oxide ceramic electrolyte composite material of claim 1 in solid oxide fuel cell anode materials.
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| CN101867048A (en) * | 2010-05-10 | 2010-10-20 | 北京科技大学 | High-conductivity double perovskite aluminum-doped Sr2AlxMg1-xMoO6-Delta anode material and preparation method thereof |
| CN104388972A (en) * | 2014-10-24 | 2015-03-04 | 清华大学 | Cathode material used for solid oxide electrolytic cell and application of cathode material |
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| CN101867048A (en) * | 2010-05-10 | 2010-10-20 | 北京科技大学 | High-conductivity double perovskite aluminum-doped Sr2AlxMg1-xMoO6-Delta anode material and preparation method thereof |
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