CN112563546B - Oxygen ion conductive medium-temperature solid oxide fuel cell electrolyte and preparation method thereof - Google Patents
Oxygen ion conductive medium-temperature solid oxide fuel cell electrolyte and preparation method thereof Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 34
- 239000000446 fuel Substances 0.000 title claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 13
- 239000001301 oxygen Substances 0.000 title claims abstract description 13
- 239000007787 solid Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims description 12
- 239000000126 substance Substances 0.000 claims abstract description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 14
- -1 oxygen ion Chemical class 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 3
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Inorganic materials [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910019626 (NH4)6Mo7O24 Inorganic materials 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims 1
- 238000007599 discharging Methods 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 5
- 239000002001 electrolyte material Substances 0.000 abstract description 4
- 238000009841 combustion method Methods 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007704 transition Effects 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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
- H01M2300/0074—Ion conductive at high temperature
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Abstract
The invention adopts a sol-gel-combustion method to prepare an oxygen ion-conductive intermediate-temperature solid oxide fuel cell electrolyte with a chemical formula of Ba3NbMoO8.5. The electrolyte has the conductivity of 0.014S/cm at 800 ℃ in a dry air atmosphere, meets the requirement of a medium-temperature SOFC on electrolyte materials, and is higher than Ba prepared by a traditional solid phase method3NbMoO8.5The electrical conductivity of (1).
Description
Technical Field
The invention belongs to the field of preparation of fuel cell electrolytes, and particularly relates to an oxygen ion-conductive intermediate-temperature solid oxide fuel cell electrolyte and a preparation method thereof.
Background
Energy is a main resource in the development process of human beings, and has a decisive influence on the aspects of clothes, food, live, movement and the like of the human beings. At present, the main energy in the world is mainly fossil energy (coal, natural gas and petroleum). Due to the limited storage of the traditional fossil energy and the global ecological environment pollution, various countries in the world take practical measures to protect the environment and develop new energy. China is a large energy consumption country, and the problem of energy shortage is particularly that related technologies and methods for efficiently utilizing fuels need to be developed more urgently.
Solid Oxide Fuel Cells (SOFC) are capable of converting chemical energy present in a fuel and an oxidant directly into electrical energy. The fuel cell differs from a conventional cell in that its fuel and oxidant are not stored inside the cell but supplied from the outside, and power can be continuously generated as long as the fuel and oxidant are continuously supplied thereto. Because the combustion is not involved in the reaction process, the chemical energy in the fuel can be efficiently converted into electric energy, and the emission of pollutants is greatly reduced. The SOFC has the working temperature of 500-1000 ℃, byproducts of the SOFC are high-quality heat and water vapor, the energy utilization rate is as high as about 80% under the condition of combined heat and power supply, and the SOFC is a clean and efficient energy system. Therefore, the fuel cell is considered to be an efficient, energy-saving and environment-friendly power generation system which is expected to be the most promising of the 21 st century.
SOFC's that are currently commercially available typically operate at 1000 ℃ and at such high temperatures that SOFC's suffer from a number of problems, such as electrode densification, high interconnect material requirements, and poor cell sealing performance. Therefore, the reduction of the SOFC working temperature is a way for effectively reducing the system cost and improving the stability of the SOFC. The electrolyte material can obtain higher conductivity at the intermediate temperature so as to meet the requirements of the current intermediate-temperature SOFC electrolyte material.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and the novel Ba is prepared by adopting a sol-gel combustion method3NbMoO8.5The electrolyte has good stability under reducing conditions. After the electrolyte sheet is sintered at 1200 ℃ and is insulated for 5 hours, the conductivity at 800 ℃ can reach 0.013S/cm in a dry air atmosphere, and the requirement of a medium-temperature SOFC on the electrolyte material is met.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of oxygen ion conductive intermediate-temperature solid oxide fuel cell electrolyte with a chemical formula of Ba3NbMoO8.5The preparation is carried out by adopting a sol-gel method; the preparation method comprises the following steps:
(I) Ba3NbMoO8.5Preparing electrolyte powder:
1) push Ba3NbMoO8.5Weighing Nb according to the stoichiometric ratio2O5，Ba(NO3)2，(NH4)6Mo7O24·4H2O, weighing the ethylene glycol and the citric acid according to the molar ratio of the metal cations to the ethylene glycol and the citric acid of 1:2: 2;
2) mixing Ba (NO)3)2，(NH4)6Mo7O24·4H2Adding O and citric acid into distilled waterDissolving;
3) sequentially pouring the nitrate solution obtained in the step 2) into a citric acid solution, and then adding Nb into the solution2O5Then dripping ethylene glycol;
4) dropwise adding ammonia water with the mass concentration of 15% -20% into the solution to adjust the pH value of the solution to 7-8;
5) heating the mixed solution obtained in the step 4) to 80 ℃ in a constant-temperature magnetic stirrer, and then continuously stirring the mixed solution at 80 ℃ until gel is formed;
6) transferring the gel into an evaporating dish, and heating on an electric furnace until fluffy oxide powder is formed;
7) heating the obtained oxide powder to 600 + -10 deg.C, maintaining for 2 + -0.1 hr to remove residual organic matter, maintaining at 1200 + -10 deg.C for 10 + -0.1 hr, and furnace cooling to obtain Ba3NbMoO8.5Powder;
(di) Ba3NbMoO8.5Preparing an electrolyte sheet:
prepared Ba3NbMoO8.5Ball-milling the powder for 6-8h, drying, adding a proper amount of PVB (10 wt.%) as a bonding agent, uniformly grinding, pouring a proper amount of PVB into a mold, pressing into a wafer under the pressure of 150MPa, heating the wafer to 500 +/-10 ℃ at the speed of 3 ℃/min, preserving heat for 1h for binder removal, heating to 1200 +/-10 ℃ at the speed of 3 ℃/min, preserving heat for 5 +/-0.1 h, and obtaining compact Ba3NbMoO8.5An electrolyte wafer.
The invention has the beneficial effects that:
(1) ba of the invention3NbMoO8.5The pure oxygen ion conductor has good stability and electrochemical performance, can be used as an ideal solid electrolyte of IT-SOFCs, is a novel hexagonal perovskite structure, and can be fitted by using a mixed model of cordierite and a 9R structure. Ba3NbMoO8.5Is a material with excellent oxygen ion conduction found for the first time in the structure family, Ba, Nb and Mo jointly form the structure, wherein Nb and Mo elements and O jointly form (Mo/Nb) O6Octahedron and (Mo/Nb) O4Tetrahedron, not toThe two elements are obtained by doping and replacing the position of one element. The continuous transition from octahedra to tetrahedra with increasing temperature is the main reason for the increased conductivity.
(2) Ba of the invention3NbMoO8.5Has not been doped and compounded, is very stable in acid gas and water vapor atmosphere and is more CeO than CeO under the reducing condition2The base oxide conductor has wider stability range, avoids electron conduction introduced by Ce element reduction, and is expected to obtain higher open-circuit voltage under the SOFC working condition. Based on the material, the material has good prospect in SOFC application.
(3) The invention adopts a sol-gel-combustion method to prepare Ba with high ionic conductivity3NbMoO8.5Electrolyte, and conventional solid phase method for preparing Ba3NbMoO8.5Compared with the prior art, the preparation method has the advantages of shorter preparation time, simpler process, easier acquisition of pure-phase materials and more excellent electrochemical performance.
Drawings
FIG. 1 shows Ba prepared according to the present invention3NbMoO8.5XRD pattern of the tablet;
FIG. 2 shows Ba3NbMoO8.5A plot of the total conductivity of the electrolyte at different test temperatures;
FIG. 3 is an impedance spectrum of Ba3NbMoO8.5 electrolyte prepared by a solid phase method and a sol-gel method.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.
Example 1
1 mol of Ba3NbMoO8.5Preparing electrolyte powder:
1) 784.02g (3mol) Ba (NO) are weighed out3)2，176.5514g(0.1429mol)(NH4)6Mo7O24·4H2O，132.9050g(0.5mol)Nb2O5620.7g (10mol) of ethylene glycol and 2101.4g (10mol) of citric acid;
2) will be (NH)4)6Mo7O24·4H2O、Ba(NO3)2And citric acid are respectively added into distilled water for dissolution;
3) sequentially pouring the nitrate solution obtained in the step 2) into a citric acid solution, and then adding Nb into the solution2O5Then dripping ethylene glycol;
4) dropwise adding ammonia water with the concentration of 15% -20% into the solution to adjust the pH value of the solution to 7-8;
5) heating the mixed solution obtained in the step 4) to 80 ℃ in a constant-temperature magnetic stirrer, and then continuously stirring the mixed solution at 80 ℃ until gel is formed;
6) transferring the gel into an evaporating dish, and heating on an electric furnace until fluffy oxide powder is formed;
7) heating the obtained oxide powder to 600 + -10 deg.C, maintaining for 2 + -0.1 hr to remove residual organic matter, maintaining at 1200 + -10 deg.C for 10 + -0.1 hr, and furnace cooling to obtain Ba3NbMoO8.5Powder;
(di) Ba3NbMoO8.5Preparing an electrolyte sheet:
ba to be obtained in example 13NbMoO8.5Ball-milling the powder for 6-8h, drying, adding a proper amount of PVB (10 wt.%) as an adhesive, uniformly grinding, pouring 0.4g of the powder into a mould, preparing a wafer with the diameter of 12 +/-0.1 mm and the thickness of 1 +/-0.1 mm under the pressure of 150MPa, heating the wafer to 500 +/-10 ℃ at the speed of 3 ℃/min, preserving heat for 1h to remove glue, heating to 1200 +/-10 ℃ at the speed of 3 ℃/min, preserving heat for 5 +/-0.1 h to obtain compact Ba3NbMoO8.5An electrolyte wafer.
Conductivity test method:
the ac conductance of the electrolyte was measured by the two-terminal method. Ba obtained after sintering at 1200 +/-10 ℃ for 5 +/-0.1 hours3NbMoO8.5Coating silver paste on two sides of the electrolyte wafer, and then roasting for 2h at 450 ℃ to obtain the silver electrode. Silver electrodes at two ends are connected with an alternating current impedance instrument by silver wires. The adopted AC impedance meter is an Interface 1000 electrochemical workstation of the United states Gamry company, the disturbance potential is 100mV, and the frequency is measuredThe range is 0.1Hz-1MHz, the test temperature is 400-800 ℃, and the measurement is carried out in the air atmosphere at intervals of 50 ℃. The conductivity is calculated using the following formula:
wherein, sigma is electrolyte conductivity, S/cm;
h is the thickness of the electrolyte sheet in cm;
r is electrolyte resistance with unit omega;
s is the cross-sectional area of the electrolyte sheet in cm2。
FIG. 1 shows Ba prepared according to the present invention3NbMoO8.5XRD pattern of the tablet, FIG. 2 is Ba3NbMoO8.5Total conductivity plot of electrolyte at different test temperatures. From the figure, Ba is known3NbMoO8.5The conductivity reached 0.014S/cm at 800 ℃.
Comparative example 1
The traditional solid phase method comprises the following steps: mixing BaCO3，MoO3And Nb2O5The raw materials were ground, tableted and then calcined in an alumina crucible at 900 c for 10 hours. Followed by regrinding, tabletting, and heating at 1100 deg.C for 48 hours, followed by cooling to room temperature at a rate of 5 deg.C/min. The subsequent heating step was repeated until a phase pure product was obtained.
The method can obtain pure phase samples within 10 hours, shortens the preparation time by more than 48 hours compared with the traditional process, greatly shortens the production period and saves the energy consumption. Especially, the performance of the sample is better than that of the sample obtained by the traditional process.
FIG. 3 is Ba prepared by two methods3NbMoO8.5The EIS impedance spectrum at 800 ℃ in a dry air atmosphere can be visually distinguished by converting the impedance into the resistivity: ba synthesized by sol-gel method3MoNbO8.5Has smaller impedance and higher oxygen ion conductivity according to the formula
And calculating to respectively obtain the oxygen ion conductivity:
solid phase method: σ =0.013S · cm-1，
Sol-gel method: σ =0.014S · cm-1
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (5)
1. A preparation method of an oxygen ion conductive intermediate-temperature solid oxide fuel cell electrolyte is characterized by comprising the following steps: the chemical formula of the electrolyte is Ba3NbMoO8.5(ii) a The preparation method specifically comprises the following steps:
(I) Ba3NbMoO8.5Preparing electrolyte powder:
1) push Ba3NbMoO8.5Weighing Nb according to the stoichiometric ratio2O5，Ba(NO3)2，(NH4)6Mo7O24·4H2O, weighing glycol and citric acid;
2) mixing Ba (NO)3)2，(NH4)6Mo7O24·4H2Respectively adding O and citric acid into distilled water for dissolving;
3) sequentially pouring the salt solution obtained in the step 2) into a citric acid solution, and then adding Nb into the solution2O5Then dripping ethylene glycol;
4) dropwise adding ammonia water into the solution to adjust the pH value of the solution to 7-8;
5) heating the mixed solution obtained in the step 4) to 80 ℃ in a constant-temperature magnetic stirrer, and then continuously stirring the mixed solution at 80 ℃ until gel is formed;
6) transferring the gel into an evaporating dish, and heating on an electric furnace until fluffy oxide powder is formed;
7) heating the obtained oxide powder to eliminate residual organic matter, maintaining at 1200 + -10 deg.c for 10 + -0.1 hr, and cooling in furnace to form Ba3NbMoO8.5Powder of；
(di) Ba3NbMoO8.5Preparing an electrolyte sheet:
prepared Ba3NbMoO8.5Ball milling the powder, drying, adding PVB as adhesive, grinding uniformly, pouring into a mould, pressing, removing glue and heat-insulating to obtain compact Ba3NbMoO8.5An electrolyte wafer.
2. The method of making an oxygen ion conducting intermediate-temperature solid oxide fuel cell electrolyte according to claim 1, wherein: the molar ratio of the metal cations to the ethylene glycol and the citric acid in the step 1) is 1:2: 2.
3. The method of making an oxygen ion conducting intermediate-temperature solid oxide fuel cell electrolyte according to claim 1, wherein: and 4), the mass concentration of the ammonia water in the step 4) is 15-20%.
4. The method of making an oxygen ion conducting intermediate-temperature solid oxide fuel cell electrolyte according to claim 1, wherein: the step 7) of eliminating residual organic matters comprises the following specific steps: the obtained oxide powder is heated to 600 plus or minus 10 ℃ and is kept warm for 2 plus or minus 0.1 hours to eliminate residual organic matters.
5. The method of making an oxygen ion conducting intermediate-temperature solid oxide fuel cell electrolyte according to claim 1, wherein: the pressing, glue discharging and heat preservation treatment in the step (II) are specifically as follows: pressing into a wafer under the pressure of 150MPa, heating the wafer to 500 +/-10 ℃ at the speed of 3 ℃/min, preserving heat for 1h for removing glue, and then heating to 1200 +/-10 ℃ at the speed of 3 ℃/min, preserving heat for 5 +/-0.1 h.
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