CN101572313A - Cathode material for intermediate-low temperature solid oxide fuel cells and compound cathode material thereof - Google Patents
Cathode material for intermediate-low temperature solid oxide fuel cells and compound cathode material thereof Download PDFInfo
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- CN101572313A CN101572313A CNA2009100248561A CN200910024856A CN101572313A CN 101572313 A CN101572313 A CN 101572313A CN A2009100248561 A CNA2009100248561 A CN A2009100248561A CN 200910024856 A CN200910024856 A CN 200910024856A CN 101572313 A CN101572313 A CN 101572313A
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- 239000010406 cathode material Substances 0.000 title claims abstract description 61
- 239000007787 solid Substances 0.000 title claims abstract description 19
- 239000000446 fuel Substances 0.000 title claims abstract description 18
- 150000001875 compounds Chemical class 0.000 title abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 239000002131 composite material Substances 0.000 claims description 11
- 239000002001 electrolyte material Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 abstract description 33
- 239000000126 substance Substances 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 44
- 239000000843 powder Substances 0.000 description 23
- 238000000498 ball milling Methods 0.000 description 22
- 238000001354 calcination Methods 0.000 description 22
- 230000010287 polarization Effects 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 238000005303 weighing Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000002050 diffraction method Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000002847 impedance measurement Methods 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 238000010532 solid phase synthesis reaction Methods 0.000 description 7
- 244000137852 Petrea volubilis Species 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- 238000000462 isostatic pressing Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000010339 dilation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- HBAGRTDVSXKKDO-UHFFFAOYSA-N dioxido(dioxo)manganese lanthanum(3+) Chemical compound [La+3].[La+3].[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O HBAGRTDVSXKKDO-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QIMZHEUFJYROIY-UHFFFAOYSA-N [Co].[La] Chemical compound [Co].[La] QIMZHEUFJYROIY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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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
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a cathode material for intermediate-low temperature solid oxide fuel cells and a compound cathode material thereof. The cathode material has good thermal chemical stability at about 700 DEG C, and simultaneously the cathode material is attached to CeO2-based electrolyte and has good oxygen catalytic reduction. The cathode material for the intermediate-low temperature solid oxide fuel cells has the following structural formula: Sm1-xSrxFe1-yMyO3-delta, wherein M is Fe, Mn, Cu, Ni or Co; x is more than or equal to 0.3 and less than or equal to 0.9; y is more than or equal to 0 and less than or equal to 0.5; and delta is more than or equal to 0 and less than 1.
Description
Technical field
The present invention relates to a kind of battery cathode material and composite cathode material thereof, relate to a kind of intermediate temperature solid oxide fuel cell cathode material and composite cathode material thereof in particular.
Background technology
Intermediate temperature solid oxide fuel cell is a kind of efficient, eco-friendly electrical energy production mode.Because electrode activity reduces rapidly with the decline of reaction temperature, the cathode material strontium doping lanthanum manganate (LSM) that high temperature solid oxide fuel cell is commonly used has been not suitable as the electrode of ITSOFC.
As a kind of desirable ITSOFC cathode material, it should possess higher hydrogen reduction performance, with the thermal coefficient of expansion (TEC) that electrolyte is complementary, higher chemistry and structural stability, and with electrolyte compatibility is preferably arranged under operating temperature.
It is at doped Ce O that lanthanum cobalt or other relevant perovskite oxides have been proved to be
2More potential low temperature SOFC cathode material on the electrolyte, however their TEC is about 17 * 10
-6/ K is much larger than doped Ce O
2Electrolytical TEC makes these two kinds of materials be difficult in together and uses.Cause people's attention so develop a kind of work of high-performance intermediate temperature solid oxide fuel cell cathode material.
Summary of the invention
The invention solves above-mentioned problems of the prior art and deficiency, a kind of intermediate temperature solid oxide fuel cell cathode material and composite cathode material thereof are provided.
The present invention is achieved by the following technical solutions:
Intermediate temperature solid oxide fuel cell cathode material of the present invention, its structural formula are Sm
1-xSr
xFe
1-yM
yO
3-δ, wherein M is Fe, Mn, Cu, Ni or Co, 0.3≤x≤0.9,0≤y≤0.5,0≤δ＜1.
Intermediate temperature solid oxide fuel cell cathode material of the present invention, its further technical scheme are that described structural formula is Sm
1-xSr
xFe
1-yM
yO
3-δ, 0.3≤x≤0.7,0≤y≤0.2,0≤δ≤0.5 wherein.
Intermediate temperature solid oxide fuel cell cathode material of the present invention, its further again technical scheme is that described structural formula is Sm
0.5Sr
0.5FeO
3-δ, 0≤δ≤0.5 wherein.
The cathode material of the invention described above can adopt solid reaction process to synthesize, and also can adopt sol-gel process, coprecipitation etc. synthetic.
The described composite cathode material that makes of above-mentioned cathode material that utilizes of the present invention, it is composed as follows: structural formula is Sm
1-xSr
xFe
1-yM
yO
3-δCathode material and CeO
2The quality proportioning of base electrolyte material is 1: 5%～100%.
Composite cathode material of the present invention, its further technical scheme is described CeO
2The base electrolyte material structural formula is Sm
zCe
1-zO
2, wherein 0＜z＜1 (abbreviation SDC).
Composite cathode material of the present invention, its further technical scheme can also be described CeO
2The base electrolyte material structural formula is Gd
zCe
1-zO
2, wherein 0＜z＜1 (abbreviation GDC).
Composite cathode material of the present invention is to be Sm with structural formula
1-xSr
xFe
1-yM
yO
3-δCathode material powder and SDC or GDC powder be that 1: 5%～100% ratio is used ball milling 1 hour～10 hours according to mass ratio, promptly make combination electrode material after two kinds of compounds fully mix.
The electrolyte-supported body and function dry pressing of SDC (or GDC) makes simultaneously, and the electrolyte-supported body is calcined 2h to form fine and close electrolyte at 1550～1600 ℃.Then the cathode powder that makes is blended in make in the organic solvent be coated onto on the dielectric substrate behind the slurry after, calcining made the cathode layer of porous in 4 hours under the 1100-1250 degree.
The polarization resistance of negative electrode adopts the ac impedance technology test, air atmosphere, and the silver slurry is as collector.
Beneficial effect of the present invention is as follows:
Cathode material of the present invention has good thermo-chemical stability about 700 ℃, cathode material of the present invention is attached to CeO simultaneously
2Has oxygen catalytic reduction preferably on the base electrolyte; This cathode material has low thermal expansivity in addition, its thermal coefficient of expansion and CeO
2Electrolyte is close, with CeO
2Base electrolyte has good compatibility, is applicable to the intermediate temperature solid oxide fuel cell cathode material.
Description of drawings
Fig. 1 is the cathode material Sm of one embodiment of the invention
0.5Sr
0.5FeO
3-δX-ray diffraction (XRD) spectrogram.
Fig. 2 is the cathode material Sm of one embodiment of the invention
0.5Sr
0.5FeO
3-δThe relation of conductivity and temperature.
Fig. 3 is the cathode material Sm of one embodiment of the invention
0.5Sr
0.5FeO
3-δFully mix the XRD spectra of back behind 1200 ℃ of calcining 4h with the SDC electrolyte by 1: 1 mass ratio.
The cathode material Sm of one embodiment of the invention when Fig. 4 is 700 ℃
0.5Sr
0.5FeO
3-δSymmetry is attached to the AC impedance spectrogram on the SDC electrolyte.
Fig. 5 is the cathode material Sm of one embodiment of the invention
0.5Sr
0.5FeO
3-δPolarization resistance and the relation of temperature.
Fig. 6 is the cathode material Sm of one embodiment of the invention
0.5Sr
0.5FeO
3-δPolarization curve in the time of 800 ℃.
Fig. 7 is the cathode material Sm of one embodiment of the invention
0.5Sr
0.5FeO
3-δThermal expansion curve with electrolyte SDC.
Fig. 8 is the cathode material Sm of one embodiment of the invention
0.5Sr
0.5FeO
3-δInterface microscopic appearance with electrolyte SDC.
Fig. 9 is the cathode material Sm of one embodiment of the invention
0.5Sr
0.5Fe
0.8Co
0.2O
3-δThe relation of conductivity and temperature.
Figure 10 is the cathode material Sm of one embodiment of the invention
0.5Sr
0.5Fe
0.8Co
0.2O
3-δPolarization resistance and the relation of temperature.
Figure 11 is the cathode material Sm of one embodiment of the invention
0.5Sr
0.5Fe
0.8Co
0.2O
3-δThe thermal expansion curve.
Figure 12 is the cathode material Sm of one embodiment of the invention
0.5Sr
0.5Fe
0.8Ni
0.2O
3-δThe relation of conductivity and temperature.
Figure 13 is the cathode material Sm of one embodiment of the invention
0.5Sr
0.5Fe
0.8Ni
0.2O
3-δPolarization resistance and the relation of temperature.
Figure 14 is the cathode material Sm of one embodiment of the invention
0.5Sr
0.5Fe
0.8Ni
0.2O
3-δThe thermal expansion curve.
Figure 15 is the cathode material Sm of one embodiment of the invention
0.3Sr
0.7FeO
3-δThe relation of conductivity and temperature
Figure 16 is the cathode material Sm of one embodiment of the invention
0.3Sr
0.7FeO
3-δPolarization resistance and the relation of temperature
Embodiment
The Sm of the synthetic 40g of solid-phase synthesis
0.5Sr
0.5FeO
3-δ, and the test of electronic conductivity, the test of thermal expansion test and polarization.
Take by weighing the Sm of 15.8057g respectively
2O
3, 12.3826g SrCO
3With 14.4768 Fe
2O
3Be mixed in ball milling 10h in the 60mL alcohol, dry back is calcined 6h down at 1050 ℃, and the ball milling calcining once promptly gets required Sm more repeatedly
0.5Sr
0.5FeO
3-δ, standby after the ball milling drying.XRD powder diffraction method test shows has formed the pure phase perovskite structure, is illustrated in figure 1 as Sm
0.5Sr
0.5FeO
3-δXRD spectra.
Take by weighing above-mentioned electrode powder 20g, the PVA aqueous solution (5% concentration) of dropping 10% mixes back granulation press strip, again at 1200 ℃ of calcining 6h, adopts the electronic conductivity of direct current four-terminal method test electrode.Be illustrated in figure 2 as Sm
0.5Sr
0.5FeO
3-δConductivity, Sm is described
0.5Sr
0.5FeO
3-δElectronic conductivity can satisfy the instructions for use of IT-SOFC negative electrode.Its hot expansibility of strip electrode polishing back test with preparing as shown in Figure 7, illustrates Sm
0.5Sr
0.5FeO
3-δWith SDC (Sm
0.2Ce
0.8O
2) electrolytical thermal expansion is very approaching, can effectively reduce because the cathode performance that thermal dilation difference causes reduces.With Sm
0.5Sr
0.5FeO
3-δPowder fully mixes the back at 1200 ℃ of calcining 4h with the SDC electrolyte, and tests its chemical compatibility, and as shown in Figure 3, XRD shows does not have cenotype to generate, and Sm is described
0.5Sr
0.5FeO
3-δHave good chemical compatibility with the SDC electrolyte, can effectively avoid because the electrode performance that interfacial reaction causes reduces.
Use isostatic pressing method to prepare the SDC electrolyte sheet, and obtain preparation dense electrolyte sheet, electrolyte sheet is polished on sand paper with the contact of raising with electrode at 1550～1600 ℃ of calcining 2h.With Sm
0.5Sr
0.5FeO
3-δCathode powder is distributed in the organic solvent, is coated to the SDC both sides, calcines 4h at 1200 ℃ after 80 ℃ of oven dry.Ac impedance measurement adopts the Solartron1260/1287 system testing.The impedance spectrogram of 700 ℃ of tests as shown in Figure 4.Polarization resistance during different temperatures is seen Fig. 5, and the polarization curve in the time of 800 ℃ is seen Fig. 6.Fig. 8 is the Sm after testing
0.5Sr
0.5FeO
3-δElectrode microscopic appearance figure, the picture show electrode contacts closely with electrolyte, and electrode is loose structure, helps the diffusion of gas.
The Sm of the synthetic 40g of solid-phase synthesis
0.5Sr
0.5Fe
0.8Co
0.2O
3-δ, and the test of electronic conductivity, the test of thermal expansion test and polarization.
Take by weighing the Sm of 15.7621g respectively
2O
3, 13.3457g SrCO
3, 2.9987g Co
2O
3With 11.5494 Fe
2O
3Be mixed in ball milling 10h in the 60mL alcohol, dry back is calcined 6h down at 1050 ℃, and the ball milling calcining once promptly gets required Sm more repeatedly
0.5Sr
0.5Fe
0.8Co
0.2O
3-δ, standby after the ball milling drying.XRD powder diffraction method test shows has formed the pure phase perovskite structure.
Take by weighing above-mentioned electrode powder 20g, the PVA aqueous solution (5% concentration) of dropping 10% mixes back granulation press strip, again at 1200 ℃ of calcining 6h, adopts the electronic conductivity of direct current four-terminal method test electrode.Be illustrated in figure 9 as Sm
0.5Sr
0.5Fe
0.8Co
0.2O
3-δConductivity, Sm is described
0.5Sr
0.5Fe
0.8Co
0.2O
3-δElectronic conductivity can satisfy the instructions for use of IT-SOFC negative electrode.Its hot expansibility of strip electrode polishing back test with preparing as shown in figure 11, illustrates Sm
0.5Sr
0.5Fe
0.8Co
0.2O
3-δWith SDC (Sm
0.2Ce
0.8O
2) electrolytical thermal expansion is approaching, can effectively reduce because the cathode performance that thermal dilation difference causes reduces.
Use isostatic pressing method to prepare the SDC electrolyte sheet, and obtain preparation dense electrolyte sheet, electrolyte sheet is polished on sand paper with the contact of raising with electrode at 1550～1600 ℃ of calcining 2h.With Sm
0.5Sr
0.5Fe
0.8Co
0.2O
3-δCathode powder is distributed in the organic solvent, is coated to the SDC both sides, calcines 4h at 1150 ℃ after 80 ℃ of oven dry.Ac impedance measurement adopts the Solartron1260/1287 system testing.Polarization resistance during different temperatures is seen Figure 10.
The Sm of the synthetic 40g of solid-phase synthesis
0.5Sr
0.5Fe
0.8Ni
0.2O
3-δ, and the test of electronic conductivity, the test of thermal expansion test and polarization.
Take by weighing the Sm of 15.7653g respectively
2O
3, 13.3485g SrCO
3, 3.0215g Ni
2O
3With 11.5518 Fe
2O
3Be mixed in ball milling 10h in the 60mL alcohol, dry back is calcined 6h down at 1050 ℃, and the ball milling calcining once promptly gets required Sm more repeatedly
0.5Sr
0.5Fe
0.8Ni
0.2O
3-δ, standby after the ball milling drying.XRD powder diffraction method test shows has formed the pure phase perovskite structure.
Take by weighing above-mentioned electrode powder 20g, the PVA aqueous solution (5% concentration) of dropping 10% mixes back granulation press strip, again at 1200 ℃ of calcining 6h, adopts the electronic conductivity of direct current four-terminal method test electrode.Be Sm as shown in figure 12
0.5Sr
0.5Fe
0.8Ni
0.2O
3-δConductivity, Sm is described
0.5Sr
0.5Fe
0.8Ni
0.2O
3-δElectronic conductivity can satisfy the instructions for use of IT-SOFC negative electrode.Its hot expansibility of strip electrode polishing back test with preparing as shown in figure 14, illustrates Sm
0.5Sr
0.5Fe
0.8Ni
0.2O
3-δWith SDC (Sm
0.2Ce
0.8O
2) electrolytical thermal expansion is approaching, can effectively reduce because the cathode performance that thermal dilation difference causes reduces.
Use isostatic pressing method to prepare the SDC electrolyte sheet, and obtain preparation dense electrolyte sheet, electrolyte sheet is polished on sand paper with the contact of raising with electrode at 1550～1600 ℃ of calcining 2h.With Sm
0.5Sr
0.5Fe
0.8Ni
0.2O
3-δCathode powder is distributed in the organic solvent, is coated to the SDC both sides, calcines 4h at 1150 ℃ after 80 ℃ of oven dry.Ac impedance measurement adopts the Solartron1260/1287 system testing.Polarization resistance during different temperatures is seen Figure 13.
Embodiment 4
The Sm of the synthetic 40g of solid-phase synthesis
0.3Sr
0.7FeO
3-δ, and electronic conductivity test and polarization test.
Take by weighing the Sm of 15.7653g respectively
2O
3, 13.3485g SrCO
3, 3.0215g Ni
2O
3With 11.5518 Fe
2O
3Be mixed in ball milling 10h in the 60mL alcohol, dry back is calcined 6h down at 1050 ℃, and the ball milling calcining once promptly gets required Sm more repeatedly
0.5Sr
0.5Fe
0.8Ni
0.2O
3-δ, standby after the ball milling drying.XRD powder diffraction method test shows has formed the pure phase perovskite structure.
Take by weighing above-mentioned electrode powder 20g, the PVA aqueous solution (5% concentration) of dropping 10% mixes back granulation press strip, again at 1200 ℃ of calcining 6h, adopts the electronic conductivity of direct current four-terminal method test electrode.Be Sm as shown in figure 15
0.3Sr
0.7FeO
3-δConductivity, Sm is described
0.3Sr
0.7FeO
3-δElectronic conductivity can satisfy the instructions for use of IT-SOFC negative electrode.
Use isostatic pressing method to prepare the SDC electrolyte sheet, and obtain preparation dense electrolyte sheet, electrolyte sheet is polished on sand paper with the contact of raising with electrode at 1550～1600 ℃ of calcining 2h.With SSm
0.3Sr
0.7FeO
3-δCathode powder is distributed in the organic solvent, is coated to the SDC both sides, calcines 4h at 1200 ℃ after 80 ℃ of oven dry.Ac impedance measurement adopts the Solartron1260/1287 system testing.Polarization resistance during different temperatures is seen Figure 16.
Embodiment 5
The Sm of the synthetic 40g of solid-phase synthesis
0.7Sr
0.3FeO
3-δAnd electronic conductivity test and polarization test.
Take by weighing the Sm of 20.9478g respectively
2O
3, 7.6013g SrCO
3With 13.7047 Fe
2O
3Be mixed in ball milling 10h in the 60mL alcohol, dry back is calcined 6h down at 1050 ℃, and the ball milling calcining once promptly gets required Sm more repeatedly
0.7Sr
0.3FeO
3-δ, standby after the ball milling drying.XRD powder diffraction method test shows has formed the pure phase perovskite structure.
Take by weighing above-mentioned electrode powder 20g, the PVA aqueous solution (5% concentration) of dropping 10% mixes back granulation press strip, again at 1200 ℃ of calcining 6h, adopts the electronic conductivity of direct current four-terminal method test electrode.The result shows that the conductivity of sample is higher than 30S/cm in 600～800 ℃ of scopes, illustrate Sm
0.7Sr
0.3FeO
3-δElectronic conductivity can satisfy the instructions for use of IT-SOFC negative electrode.
Use isostatic pressing method to prepare the SDC electrolyte sheet, and obtain preparation dense electrolyte sheet, electrolyte sheet is polished on sand paper with the contact of raising with electrode at 1550～1600 ℃ of calcining 2h.With Sm
0.7Sr
0.3FeO
3-δCathode powder is distributed in the organic solvent, is coated to the SDC both sides, calcines 4h at 1200 ℃ after 80 ℃ of oven dry.Ac impedance measurement adopts the Solartron1260/1287 system testing.The result shows Sm
0.7Sr
0.3FeO
3-δElectrode more than 700 ℃ the time electrode polarization resistance less than 0.5 Ω cm
2, satisfy the performance requirement of SOFCs negative electrode.
Embodiment 6
The Sm of the synthetic 40g of solid-phase synthesis
0.5Sr
0.5Fe
0.8Cu
0.2O
3-δAnd electronic conductivity test and polarization test.
Take by weighing the Sm of 16.6397g respectively
2O
3, 14.0887g SrCO
3, the CuO of 3.0367g and 12.1925 Fe
2O
3Be mixed in ball milling 10h in the 60mL alcohol, dry back is calcined 6h down at 1050 ℃, and the ball milling calcining once promptly gets required Sm more repeatedly
0.5Sr
0.5Fe
0.8Cu
0.2O
3-δ, standby after the ball milling drying.XRD powder diffraction method test shows has formed the pure phase perovskite structure.
Take by weighing above-mentioned electrode powder 20g, the PVA aqueous solution (5% concentration) of dropping 10% mixes back granulation press strip, again at 1200 ℃ of calcining 6h, adopts the electronic conductivity of direct current four-terminal method test electrode.The result shows, Sm in Range of measuring temp
0.5Sr
0.5Fe
0.8Cu
0.2O
3-δConductivity all satisfies the requirement of SOFCs cathode material.
Use isostatic pressing method to prepare the SDC electrolyte sheet, and obtain preparation dense electrolyte sheet, electrolyte sheet is polished on sand paper with the contact of raising with electrode at 1550～1600 ℃ of calcining 2h.With Sm
0.5Sr
0.5Fe
0.8Cu
0.2O
3-δCathode powder is distributed in the organic solvent, is coated to the SDC both sides, calcines 4h at 1200 ℃ after 80 ℃ of oven dry.Ac impedance measurement adopts the Solartron1260/1287 system testing.The result shows Sm
0.5Sr
0.5Fe
0.8Cu
0.2O
3-δHave good electrode catalyst activity, can be as the SOFCs cathode material.
Embodiment 7
The Sm of the synthetic 40g of solid-phase synthesis
0.5Sr
0.5Fe
0.8Mn
0.2O
3-δAnd electronic conductivity test and polarization test.
Take by weighing the Sm of 15.8186g respectively
2O
3, 13.3936g SrCO
3, 3.1550g MnO
2With 11.5909 Fe
2O
3Be mixed in ball milling 10h in the 60mL alcohol, dry back is calcined 6h down at 1050 ℃, and the ball milling calcining once promptly gets required Sm more repeatedly
0.5Sr
0.5Fe
0.8Mn
0.2O
3-δ, standby after the ball milling drying.XRD powder diffraction method test shows has formed the pure phase perovskite structure.Adopt the electronic conductivity of direct current four-terminal method test electrode, ac impedance measurement shows that this material has good electrode catalyst activity, can be as the SOFCs cathode material.
Claims (6)
1, a kind of intermediate temperature solid oxide fuel cell cathode material is characterized in that structural formula is Sm
1-xSr
xFe
1-yM
yO
3-δ, wherein M is Fe, Mn, Cu, Ni or Co, 0.1≤x≤1,0≤y≤0.5,0≤δ＜1.
2, intermediate temperature solid oxide fuel cell cathode material according to claim 1 is characterized in that its structural formula is Sm
1-xSr
xFe
1-yM
yO
3-δ, 0.3≤x in its formula≤0.7,0≤y≤0.2,0≤δ≤0.5.
3, intermediate temperature solid oxide fuel cell cathode material according to claim 2 is characterized in that its structural formula is Sm
0.5Sr
0.5FeO
3-δ, 0≤δ≤0.5 wherein.
4, a kind of composite cathode material that makes as the arbitrary described intermediate temperature solid oxide fuel cell cathode material of claim 1-3 that utilizes is characterized in that it is composed as follows:
Intermediate temperature solid oxide fuel cell cathode material and CeO
2The quality proportioning of base electrolyte material is 1: 0.05～0.95.
5, composite cathode material according to claim 4 is characterized in that described CeO
2The base electrolyte material structural formula is Sm
zCe
1-zO
2, 0＜z＜1 wherein.
6, composite cathode material according to claim 4 is characterized in that described CeO
2The base electrolyte material structural formula is Gd
zCe
1-zO
2, 0＜z＜1 wherein.
Priority Applications (1)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180523A (en) * | 2011-02-01 | 2011-09-14 | 吉林大学 | Cathode material of mesotherm solid oxide fuel battery and preparation method thereof |
| CN102208663A (en) * | 2011-04-20 | 2011-10-05 | 南京工业大学 | Transition metal element B site-doped BaFeO3-delta-based ABO3 type perovskite fuel cell cathode material and application thereof |
| CN109360991A (en) * | 2018-11-01 | 2019-02-19 | 东北大学 | A kind of low-temperature solid oxide fuel cell composite cathode and preparation method thereof |
| 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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2009
- 2009-02-27 CN CNA2009100248561A patent/CN101572313A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180523A (en) * | 2011-02-01 | 2011-09-14 | 吉林大学 | Cathode material of mesotherm solid oxide fuel battery and preparation method thereof |
| CN102180523B (en) * | 2011-02-01 | 2012-07-04 | 吉林大学 | Cathode material of mesotherm solid oxide fuel battery and preparation method thereof |
| CN102208663A (en) * | 2011-04-20 | 2011-10-05 | 南京工业大学 | Transition metal element B site-doped BaFeO3-delta-based ABO3 type perovskite fuel cell cathode material and application thereof |
| CN109360991A (en) * | 2018-11-01 | 2019-02-19 | 东北大学 | A kind of low-temperature solid oxide fuel cell composite cathode and preparation method thereof |
| CN109360991B (en) * | 2018-11-01 | 2021-12-14 | 东北大学 | Low-temperature solid oxide fuel cell composite cathode and preparation method thereof |
| 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 |
| CN115180937B (en) * | 2022-08-01 | 2023-09-22 | 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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