CN102208663A - BaFeO doped with transition metal element at B position3-δABO of radicals3Perovskite type fuel cell cathode material and application thereof - Google Patents
BaFeO doped with transition metal element at B position3-δABO of radicals3Perovskite type fuel cell cathode material and application thereof Download PDFInfo
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- 239000010406 cathode material Substances 0.000 title claims abstract description 38
- 239000000446 fuel Substances 0.000 title claims abstract description 27
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 238000003980 solgel method Methods 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 abstract description 10
- -1 oxygen ions Chemical class 0.000 abstract description 4
- 230000010757 Reduction Activity Effects 0.000 abstract description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 23
- 239000000843 powder Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 239000003570 air Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 238000000498 ball milling Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 5
- 238000002050 diffraction method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 238000000713 high-energy ball milling Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000012080 ambient air Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000006257 cathode slurry Substances 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000003836 solid-state method Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000010345 tape casting Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NGWKGSCSHDHHAJ-YPFQVHCOSA-N Liquoric acid Chemical compound C1C[C@H](O)C(C)(C)C2CC[C@@]3(C)[C@]4(C)C[C@H]5O[C@@H]([C@](C6)(C)C(O)=O)C[C@@]5(C)[C@@H]6C4=CC(=O)C3[C@]21C NGWKGSCSHDHHAJ-YPFQVHCOSA-N 0.000 description 2
- NGWKGSCSHDHHAJ-UHFFFAOYSA-N Liquoric acid Natural products C1CC(O)C(C)(C)C2CCC3(C)C4(C)CC5OC(C(C6)(C)C(O)=O)CC5(C)C6C4=CC(=O)C3C21C NGWKGSCSHDHHAJ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000011532 electronic conductor Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 241000968352 Scandia <hydrozoan> Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910001938 gadolinium oxide Inorganic materials 0.000 description 1
- 229940075613 gadolinium oxide Drugs 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011533 mixed conductor Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- HJGMWXTVGKLUAQ-UHFFFAOYSA-N oxygen(2-);scandium(3+) Chemical compound [O-2].[O-2].[O-2].[Sc+3].[Sc+3] HJGMWXTVGKLUAQ-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001954 samarium oxide Inorganic materials 0.000 description 1
- 229940075630 samarium oxide Drugs 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000005303 weighing 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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- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
BaFeO doped with transition metal element B site3-δABO of radicals3A perovskite fuel cell cathode material, characterized in that the molecular formula of the material is BaMxFe1-xO3-δThe perovskite oxide of (a); wherein M is one of Ti, V, Cr, Mn, Ni, Cu, Zn, Zr, Nb or Mo; x is more than 0 and less than 1; delta is the oxygen vacancy concentration, delta is more than-1 and less than 1. The cathode material has matched thermal expansion coefficients with traditional electrolytes such as YSZ, SDC and the like, and shows mixed conductivity of oxygen ions and electrons in air atmosphere. The material shows good oxygen reduction activity in the temperature range of 500-800 ℃, and is suitable for medium-low temperature solid oxide fuel cells.
Description
Technical field
The invention belongs to the fuel cell technology field, be specifically related to the BaFeO that mixes in a kind of a small amount of transition metal B position
3-δThe ABO of base
3Type perovskite intermediate temperature solid oxide fuel cell cathode material.
Background technology
Solid Oxide Fuel Cell is converted into electric energy as a kind of electrochemical energy conversion equipment with the chemical energy in the fuel, has energy conversion efficiency height and pollutant emission and waits outstanding advantage less.Traditional SOFC cathode material is La
1-xSr
xMnO
3(LSM), because itself and Y
2O
3Stable ZrO
2(YSZ) electrolyte has excellent compatibility, high chemistry and outstanding advantage such as structural stability and highly electron conductive, and it remains high temperature cathode material the most commonly used at present.The distinguishing feature of LSM is not have under the situation of polarization current to be pure electronic conductor, thereby oxygen is confined to electrode-electric in the electrochemical reduction strictness on the battery that with LSM is negative electrode and separates on matter-air three phase boundary.When operating temperature reduced, LSM cathodic polarization resistance sharply rose, and people generally believe at LSM cathode material below 800 ℃ and just are not suitable for using.The middle cryogenic property that how to improve negative electrode becomes the key point of low temperatureization among the present SOFC.Adopt mixed oxygen ion electronic conductor oxide as cathode material, can successfully the electrode reaction zone be expanded to the surface of entire electrode from traditional three phase boundary, and then improved electrode greatly at low temperatures to the activity function of oxygen, thereby the mixed conductive cathode material of development of new becomes the most popular research field of Solid Oxide Fuel Cell low temperatureization in recent years.At present the mixed conductor oxide mostly is and contains cobalt/cobalt oxide, and its outstanding feature is that reduction has good catalytic activity to the oxygen electrochemical reaction, but this type of contains cobalt/cobalt oxide and all has higher thermal coefficient of expansion and lower steady chemical structure usually.Non-cobalt-based negative electrode is compared with the LSM negative electrode, has higher chemical property when middle low temperature, compares with the perovskite-type material that contains cobalt, has low thermal coefficient of expansion again, and high chemical stability and thermal stability are the very potential cathode materials of a class.
Summary of the invention
The BaFeO that the object of the invention provides a kind of transition metal B position to mix for the deficiency of improving existing intermediate temperature solid oxide fuel cell cathode material
3-δThe ABO of base
3Type perovskite fuel battery cathode material makes it have higher hydrogen reduction catalytic activity under middle low temperature; Another object of the present invention also provides the application of above-mentioned battery cathode material in the intermediate temperature solid oxide fuel cell cathode material.
Technical scheme of the present invention is: the BaFeO that mixes in a kind of transition metal B position
3-δThe ABO of base
3Type perovskite fuel battery cathode material, the molecular formula that it is characterized in that described material is BaM
xFe
1-xO
3-δPerovskite oxide; Wherein M is a kind of of Ti, V, Cr, Mn, Ni, Cu, Zn, Zr, Nb or Mo; 0＜x＜1; δ is an oxygen vacancies concentration ,-1＜δ＜1.Preferred 0.05≤x≤0.2;-0.5＜δ＜0.5.
The present invention is at BaFeO
3-δThe B position of base is carried out transition metal element doped on a small quantity, can improve the performance of cathode material, and the hybrid conductive performance of reinforcing material, these advantages make material of the present invention become the ideal material of intermediate temperature solid oxide fuel cell negative electrode.
Material of the present invention can adopt solid reaction process to synthesize, and also can adopt sol-gel process synthetic.If with solid phase method synthetic material of the present invention, according to target product B aM
xFe
1-xO
3-δThe metering ratio of (0＜x＜1 ,-1＜δ＜1) chemical formula is with the BaCO of certain mass
3(analyzing pure), Fe
2O
3(analyzing pure) and M
2O
x(analyzing pure) mixes, with alcohol or acetone is medium, at high-energy ball milling instrument (FRITSCH, Pulverisette 6) middle ball milling 1-5 hour, up to mixing, further mixture is evaporated cured down at 200-250 ℃, to be dried fully after, obtain presoma, at last with presoma at 1100-1350 ℃ of following roasting 5-20h, promptly get the powder of required cathode material.If with sol-gel process synthetic material of the present invention, according to target product B aM
xFe
1-xO
3-δThe metering ratio of (0.05≤x≤0.2 ,-0.5＜δ＜0.5) chemical formula is with the Ba (NO of certain mass
3)
2, Fe (NO
3)
3, M (NO
3)
xSolution adds in the deionized water, it is even that stirring makes it, again by metal population of ions: EDTA: citric acid (mol ratio)=1～2: 1～2: 2～4 amount takes by weighing EDTA and citric acid respectively, EDTA is dissolved in ammoniacal liquor and stirs and to pour in the nitrate solution that has prepared after making it to dissolve fully, the pH value that adds citric acid again and come regulator solution with ammoniacal liquor is between the 6-8, heating is stirred to and forms transparent colloidal sol, further colloidal sol is placed air dry oven, obtain solid precursor behind the dry 5-10h down at 200-250 ℃, then solid precursor is put into Muffle furnace, 800-1100 ℃ of roasting 2-20h in air atmosphere promptly gets the powder of required cathode material.
The present invention also provides the application of above-mentioned battery cathode material in the intermediate temperature solid oxide fuel cell cathode material.
Material of the present invention can be applicable to the cathode material of Solid Oxide Fuel Cell.Make the battery sheet of anode-supported with The tape casting, anode is to be that 50-100%NiO and 0-50%YSZ ball milling mix by mass fraction.The electrolyte of anode-supported is calcined 5-10h down to form fine and close electrolytic thin-membrane at 1200-1500 ℃.Then the cathode powder that makes is blended in the organic solvent, make spray on the dielectric substrate after the cathode slurry after, 1000-1200 ℃ down calcining 1-5h make the cathode layer of porous.
The electrolyte of the battery of the present invention design adopts the zirconia (YSZ) or in the lanthanum gallium based perovskite type oxide (as LSGM) one or both of zirconia (ScSZ), the stabilized with yttrium oxide of cerium oxide (YDC), gadolinium oxide doping of cerium oxide (GDC), the scandia stabilized of samarium oxide doping of cerium oxide (SDC), Yttrium oxide doping.
The designed Solid Oxide Fuel Cell of the present invention can adopt tubular type or flat design, and battery configuration can adopt anode support type or electrolyte-supporting type, and the operating temperature of battery is between 500-800 ℃.
The I-V curve test of fuel cell is to act as a fuel with hydrogen, and ambient air is as oxidant, and the digital instrument of controlling by computer records, and the flow of hydrogen is that elargol is as current collector by flow controller control.
Beneficial effect
Cathode material of the present invention and YSZ, SDC etc. are traditional, and electrolyte has matched coefficient of thermal expansion, has compatibility preferably, shows oxonium ion and electronics mixed conductivity in air atmosphere.This material shows good oxygen catalytic reduction activity in 500-800 ℃ of temperature range, be applicable to the cathode material of intermediate temperature solid oxide fuel cell.
Description of drawings
Fig. 1 is institute's invention material (a) BaNb
xFe
1-xO
3-δ(x=0,0.05,0.1,0.2) and (b) BaZn
xFe
1-xO
3-δThe X-ray diffraction curve chart of (x=0.05,0.1).
Fig. 2 is the BaNb in the embodiment of the invention 6
0.05F
E0.95O
3-δThe material coefficient of thermal expansion performance map.
Fig. 3 is the BaZn in the embodiment of the invention 7
xFe
1-xO
3-δThe hybrid conductive performance figure of (x=0,0.05,0.1) material.
Fig. 4 is the BaNb in the embodiment of the invention 8
0.1Fe
0.9O
3-δMaterial is as the I-V and the I-P curve chart of the monocell of negative electrode.
Fig. 5 is the BaZn in the embodiment of the invention 9
0.05Fe
0.95O
3-δMaterial is as the I-V and the I-P curve chart of the monocell of negative electrode.
Fig. 6 is the BaZn in the embodiment of the invention 9
0.05Fe
0.95O
3-δMaterial is as the SEM image in the monocell cross section of negative electrode.
Embodiment
Material involved in the present invention comprises but is not limited to material in following examples.
Embodiment 1:BaNb
0.05Fe
0.95O
3-δThe preparation of cathode material (solid phase method)
BaNb
0.05Fe
0.95O
3-δSynthetic by high temperature solid-state method.Proportion of products according to target is with the BaCO of stoichiometric proportion
3(analyzing pure), Nb
2O
3(analyzing pure), Fe
2O
3(analyzing pure) mixes, with alcohol or acetone is medium, at high-energy ball milling instrument (FRITSCH, Pulverisette 6) in ball milling 1 hour, up to mixing, further with mixture 250 ℃ of evaporation cured down, to be dried fully after, obtain presoma, at last with presoma at 1250 ℃ of following roasting 10h, promptly get required BaNb
0.05Fe
0.95O
3-δCathode material, wherein-0.5＜δ＜0.5.XRD powder diffraction method shown in Fig. 1 (a) is measured and is shown BaNb
0.05Fe
0.95O
3-δFormed the perovskite structure of pure phase.
Embodiment 2:BaNb
0.1Fe
0.9O
3-δThe preparation of cathode material (solid phase method)
BaNb
0.1Fe
0.9O
3-δSynthetic by high temperature solid-state method.Proportion of products according to target is with the BaCO of stoichiometric proportion
3(analyzing pure), Nb
2O
3(analyzing pure), Fe
2O
3(analyzing pure) mixes, with alcohol or acetone is medium, at high-energy ball milling instrument (FRITSCH, Pulverisette 6) in ball milling 2 hours, up to mixing, further with mixture 240 ℃ of evaporation cured down, to be dried fully after, obtain presoma, at last with presoma at 1300 ℃ of following roasting 5h, promptly get required BaNb
0.1Fe
0.9O
3-δCathode material, wherein-0.5＜δ＜0.5.XRD powder diffraction method shown in Fig. 1 (a) is measured and is shown BaNb
0.1Fe
0.9O
3-δFormed the perovskite structure of pure phase.
Embodiment 3:BaNb
0.2Fe
0.8O
3-δThe preparation of cathode material (solid phase method)
BaNb
0.2Fe
0.8O
3-δSynthetic by high temperature solid-state method.Proportion of products according to target is with the BaCO of stoichiometric proportion
3(analyzing pure), Nb
2O
3(analyzing pure), Fe
2O
3(analyzing pure) mixes, with alcohol or acetone is medium, at high-energy ball milling instrument (FRITSCH, Pulverisette 6) in ball milling 3 hours, up to mixing, further with mixture 200 ℃ of evaporation cured down, to be dried fully after, obtain presoma, at last with presoma at 1350 ℃ of following roasting 20h, promptly get required BaNb
0.2Fe
0.8O
3-δCathode material, wherein-0.5＜δ＜0.5.XRD powder diffraction method shown in Fig. 1 (a) is measured and is shown BaNb
0.2Fe
0.8O
3-δFormed the perovskite structure of pure phase.
Embodiment 4:BaZn
0.05Fe
0.09O
3-δThe preparation of cathode material (sol-gel process)
BaZn
0.05Fe
0.09O
3-δSynthetic by EDTA-citric acid associating complexometry, this synthetic method belongs to sol-gel process.With Ba (NO
3)
2, Zn (NO
3)
2, Fe (NO
3)
3According to target proportion of products is dissolved in deionized water, is made into the nitrate solution of mixing.According to metal ion sum: EDTA: the mol ratio of citric acid is to add an amount of EDTA-ammoniacal liquor and citric acid at 1: 1: 2, and the pH value to 7 of coming regulator solution with ammoniacal liquor, on 120 ℃ of heating stations, evaporate and remove moisture and make it to become gel stirring precursor aqueous solution after the clarification, place air dry oven to obtain solid precursor behind the dry 8h down then at 230 ℃, with solid precursor 1000 ℃ of roasting 5h in Muffle furnace, promptly get required BaZn at last
0.05Fe
0.09O
3-δCathode powder, wherein-0.5＜δ＜0.5.XRD powder diffraction method shown in Fig. 1 (b) is measured and is shown BaZn
0.05Fe
0.09O
3-δFormed the perovskite structure of pure phase.
Embodiment 5:BaZn
0.1Fe
0.9O
3-δThe preparation of cathode material (sol-gel process)
BaZn
0.1Fe
0.9O
3-δSynthetic by EDTA-citric acid associating complexometry, this synthetic method belongs to sol-gel process.With Ba (NO
3)
2, Zn (NO
3)
2, Fe (NO
3)
3According to target proportion of products is dissolved in deionized water, is made into the nitrate solution of mixing.According to metal ion sum: EDTA: the mol ratio of citric acid is to add an amount of EDTA-ammoniacal liquor and citric acid at 1: 1.5: 3, and the pH value to 6 of coming regulator solution with ammoniacal liquor, on 150 ℃ of heating stations, evaporate and remove moisture and make it to become gel stirring precursor aqueous solution after the clarification, place air dry oven to obtain solid precursor behind the dry 5h down then at 250 ℃, with solid precursor 950 ℃ of roasting 10h in Muffle furnace, promptly get required BaZn at last
0.1Fe
0.9O
3-δCathode powder, wherein-0.5＜δ＜0.5.XRD powder diffraction method shown in Fig. 1 (b) is measured and is shown BaZn
0.1Fe
0.9O
3-δFormed the perovskite structure of pure phase.
Embodiment 6:BaNb
0.05Fe
0.95O
3-δThe material coefficient of thermal expansion test
Electrode and electrolytical thermal coefficient of expansion need mate to guarantee the long-time stable operation of Solid Oxide Fuel Cell.Adopt Netsch DIL 402C/3/G thermal dilatometer to measure BaNb
0.05Fe
0.95O
3-δThe material coefficient of thermal expansion coefficient (Thermal Expansion Coefficient, TEC).Obtain bar shaped sample idiosome by dry pressing, be of a size of 2 * 5 * 12mm, obtain fine and close sample through 1200 ℃ of sintering, Range of measuring temp is 25-1000 ℃, and atmosphere is air, and heating rate is 5 ℃ of min
-1Fig. 2 is BaNb
0.05Fe
0.95O
3-δThe material coefficient of thermal expansion curve shows this cathode material and YSZ, and traditional electrolyte such as SDC has good thermal expansion matching.
Embodiment 7:BaZn
xFe
1-xO
3-δThe hybrid conductive performance test of (x=0,0.05,0.1) material
Adopt DC four point probe method test b aZn
xFe
1-xO
3-δThe mixed conductivity of (x=0,0.05,0.1) dense ceramic membrane, wherein the sample of x=0 as a comparison case.The preparation of bar shaped sample is identical with MEASURING THE THERMAL EXPANSION COEFFICIENT, the two ends of the bar-shaped sample behind sintering are coated the silver slurry and are connected with filamentary silver, at 200 ℃ of left and right sides heat treatment 0.5h, connect other two filamentary silvers in the middle of the sample, coat behind the silver slurry again in 200 ℃ of left and right sides heat treatment 0.5h.Testing sample is placed tube furnace, reduce to 300 ℃ from 900 ℃ and measure, rate of temperature fall is 5 ℃ of min
-1, every data point of 10 ℃ of measurements, be 2min stabilization time, test atmosphere is air, the omnidistance LabView software program control by independent development of test.As shown in Figure 3, under air atmosphere, BaZn
xFe
1-xO
3-δShow oxonium ion and electronics mixed conductivity.
Embodiment 8:BaNb
0.1Fe
0.9O
3-δMaterial is as the battery testing of negative electrode
Making with YSZ/SDC with The tape casting is the battery sheet of the anode-supported of electrolytical bilayer electrolyte, and anode is mixed by 60%NiO and 40%YSZ ball milling, and the electrolyte of anode-supported is calcined 5h down to form fine and close electrolytic thin-membrane at 1400 ℃.Then with the BaNb that makes
0.1Fe
0.9O
3-δPowder is blended in ethylene glycol, isopropyl alcohol and the glycerine, make to spray to dielectric substrate after the cathode slurry and get on, 1000 ℃ down calcining 2h make the cathode layers of porous.
The I-V curve test of fuel cell is to act as a fuel with hydrogen, and ambient air is as oxidant, and the digital instrument of controlling by computer records, and the flow of hydrogen is controlled by flow controller, and elargol is as current collector.The I-V curve that records as shown in Figure 4, the open circuit voltage in the time of 750 ℃ reaches 1.10V, illustrates that the sealing of battery is better, power density reaches 1170mW/cm
2
Embodiment 9:BaZn
0.05Fe
0.95O
3-δMaterial is as the battery testing of negative electrode
Making with YSZ/SDC with The tape casting is the battery sheet of the anode-supported of electrolytical bilayer electrolyte, and anode is mixed by 60%NiO and 40%YSZ ball milling, and the electrolyte of anode-supported is calcined 5h down to form fine and close electrolytic thin-membrane at 1400 ℃.Then with the BaZn that makes
0.05Fe
0.95O
3-δPowder is blended in ethylene glycol, isopropyl alcohol and the glycerine, make to spray to dielectric substrate after the cathode slurry and get on, 1000 ℃ down calcining 2h make the cathode layers of porous.
The I-V curve test of fuel cell is to act as a fuel with hydrogen, and ambient air is as oxidant, and the digital instrument of controlling by computer records, and the flow of hydrogen is controlled by flow controller, and elargol is as current collector.The I-V curve that records as shown in Figure 5, the open circuit voltage in the time of 750 ℃ reaches 1.09V, illustrates that the sealing of battery is better, power density reaches 1290mW/cm
2
Claims (4)
1. the BaFeO that mixes of a transition metal B position
3-δThe ABO of base
3Type perovskite fuel battery cathode material, the molecular formula that it is characterized in that described material is BaM
xFe
1-xO
3-δPerovskite oxide; Wherein M is a kind of of Ti, V, Cr, Mn, Ni, Cu, Zn, Zr, Nb or Mo; 0＜x＜1; δ is an oxygen vacancies concentration ,-1＜δ＜1.
2. cathode material according to claim 1 is characterized in that described 0.05≤x≤0.2;-0.5＜δ＜0.5.
3. cathode material according to claim 1 is characterized in that adopting sol-gel process or solid reaction process synthetic.
4. the application of battery cathode material in the intermediate temperature solid oxide fuel cell cathode material according to claim 1.
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| CN103985880A (en) * | 2014-06-04 | 2014-08-13 | 哈尔滨工业大学 | BaFeO3-theta-base B-site Bi2O3 doping solid oxide fuel cell cathode material as well as preparation method and application thereof |
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| CN112250116A (en) * | 2020-10-21 | 2021-01-22 | 合肥市盛文信息技术有限公司 | Preparation method of anode material of solid oxide fuel cell |
| CN113451594A (en) * | 2020-03-26 | 2021-09-28 | 中国科学院宁波材料技术与工程研究所 | Cathode material of solid oxide fuel cell and preparation method thereof |
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| CN102842723A (en) * | 2012-09-18 | 2012-12-26 | 黑龙江大学 | Intermediate temperature solid oxide fuel cell cathode material with perovskite structure and preparation method thereof |
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| CN111261885A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Application of oxide with three-side structure in cathode of solid oxide fuel cell |
| CN111261885B (en) * | 2018-11-30 | 2021-01-15 | 中国科学院大连化学物理研究所 | Application of oxide with three-side structure in cathode of solid oxide fuel cell |
| CN110993928A (en) * | 2019-11-19 | 2020-04-10 | 宁波大学 | Method for manufacturing lithium-sulfur battery positive electrode material |
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| CN112250116A (en) * | 2020-10-21 | 2021-01-22 | 合肥市盛文信息技术有限公司 | Preparation method of anode material of solid oxide fuel cell |
| CN112250116B (en) * | 2020-10-21 | 2023-10-13 | 合肥市盛文信息技术有限公司 | Preparation method of anode material of solid oxide fuel cell |
| CN115180937A (en) * | 2022-08-01 | 2022-10-14 | 上海电力大学 | Gadolinium and copper co-doped barium ferrite perovskite structure anode material and preparation method thereof |
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