CN101043079A - Medium-high temperature solid oxide fuel cell cathode material - Google Patents
Medium-high temperature solid oxide fuel cell cathode material Download PDFInfo
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- CN101043079A CN101043079A CNA2007100218054A CN200710021805A CN101043079A CN 101043079 A CN101043079 A CN 101043079A CN A2007100218054 A CNA2007100218054 A CN A2007100218054A CN 200710021805 A CN200710021805 A CN 200710021805A CN 101043079 A CN101043079 A CN 101043079A
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- cathode material
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- high temperature
- oxide fuel
- solid oxide
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- 239000010406 cathode material Substances 0.000 title claims abstract description 39
- 239000000446 fuel Substances 0.000 title claims abstract description 16
- 239000007787 solid Substances 0.000 title claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 20
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 18
- 239000002001 electrolyte material Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 3
- 229910003099 (Y2O3)x(ZrO2)1−x Inorganic materials 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 238000010531 catalytic reduction reaction Methods 0.000 abstract 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 54
- 239000000843 powder Substances 0.000 description 18
- 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 15
- 238000005303 weighing Methods 0.000 description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000002050 diffraction method Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910002207 La0.8Sr0.2MnO3–δ Inorganic materials 0.000 description 5
- 229910002206 La0.8Sr0.2MnO3−δ Inorganic materials 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 238000000713 high-energy ball milling Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- QIMZHEUFJYROIY-UHFFFAOYSA-N [Co].[La] Chemical compound [Co].[La] QIMZHEUFJYROIY-UHFFFAOYSA-N 0.000 description 3
- 239000012080 ambient air Substances 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
- 229910052684 Cerium Inorganic materials 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229910002204 La0.8Sr0.2MnO3 Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000006257 cathode slurry Substances 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 241000220317 Rosa Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- -1 oxonium ion Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010792 warming 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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- Inorganic Compounds Of Heavy Metals (AREA)
- Fuel Cell (AREA)
Abstract
The invention relates to a medium-high temperature solid oxide fuel cell cathode material and a composite cathode of the medium-high temperature solid oxide fuel cell cathode material and a zirconium-based electrolyte material. The molecular formula is 1－xSrx)a(ScyMn1－y)bO3－δWherein x is more than 0.01 and less than 1, y is more than 0.01 and less than 1, and a/b is more than 0.8 and less than 1.2; -0.5 < delta < 0.5. The cathode material has good thermal and chemical stability and oxygen catalytic reduction performance at about 800 ℃, has a thermal expansion coefficient close to that of a zirconium-based electrolyte, and is suitable for a medium-high temperature Solid Oxide Fuel Cell (SOFC) cathode material.
Description
Technical field
The present invention relates to a kind of in the high temperature solid oxide fuel cell cathode material and with the composite cathode of zirconium base electrolyte material.
Background technology
So far, based on the electrolyte of zirconium base, because its mechanical performance and oxidation-reduction stability are preferably still being represented electrolyte the most ripe in the SOFC electrolyte.Electrolyte and La that ionic conductivity that let it be is to the greatest extent mixed than cerium
0.8Sr
0.2Ga
0.8Mg
0.2O
3Electrolyte is all low, and the zirconium base electrolyte battery impedance of film-type (5-10 μ m) is for battery-operated still acceptable.On the other hand, the activation energy that the hydrogen reduction process need is higher, this can make cathodic polarization resistance sharply raise when operating temperature descends.Developing high performance negative electrode is the key that realizes film-type electrolyte SOFC.This work is exactly the cathode material for solid-oxide fuel cell that is conceived to develop based on the zirconium base electrolyte.
As a kind of desirable SOFC 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 this operating temperature.La
0.8Sr
0.2MnO
3(LSM) because itself and YSZ electrolyte have close TEC and better chemical compatibility, be maximum cathode material of in SOFC, using.Yet the oxygen ionic conductivity of LSM is very low, and the reduction of oxygen is subjected to the restriction of electrolyte-electrode-gas three phase boundary.When operating temperature reduced, cathodic polarization resistance sharply rose, and thought that therefore this material is not suitable in operation below 800 ℃.It is more potential low temperature SOFC cathode material on the electrolyte that cerium mixes that the perovskite oxide that lanthanum cobalt or other are relevant has been proved to be; These materials have oxygen ionic conductivity and electronic conductance at low temperatures simultaneously can make the chemical reaction zone territory be diffused into the surface of whole negative electrode-gas from the three phase boundary of routine.Yet they are incompatible with the zirconium base electrolyte.With the lanthanum cobalt is that the material of negative electrode is easy to and the zirconium base electrolyte forms insulation La mutually
2Zr
2O
7The TEC of lanthanum cobalt is about 17 * 10 in addition
-6K
-1,, make these two kinds of materials be difficult in together and use much larger than the TEC of zirconium base electrolyte.
Summary of the invention
The objective of the invention is to provide in order to improve above-mentioned the deficiencies in the prior art a kind of new cathode material with perovskite structure and with the composite cathode material of zirconium base electrolyte material.
Technical scheme of the present invention is: a spot of Sc
3+Be doped to La
0.8Sr
0.2MnO
3(LSM) in the B position Mn element, can greatly improve the performance of cathode material.And Sc
3+Doping can also reduce the TEC of material and increase the stability of material under reducing atmosphere.These above-mentioned advantages make LSSM become the ideal material based on the SOFC of zirconium base electrolyte.
Concrete technical scheme of the present invention is: the cathode material of high temperature solid oxide fuel cell in a kind of is characterized in that its molecular formula is (La
1-xSr
x)
a(Sc
yMn
1-y)
bO
3-δ(LSSM) cathode material, wherein 0.01＜x＜1,0.01＜y＜1,0.8＜a/b＜1.2;-0.5＜δ＜0.5.Preferred molecular formula is La
0.8Sr
0.2Sc
0.1Mn
0.9O
3-δThe cathode material of (0.5＜δ＜0.5).
The present invention also provides a kind of composite cathode material that contains above-mentioned cathode material, it is characterized in that composite cathode material is that molecular formula is (La
1-xSr
x)
a(Sc
yMn
1-y)
bO
3-δThe composite material of cathode material (LSSM) and zirconium base electrolyte material, wherein 0.01＜x＜1,0.01＜y＜1,0.8＜a/b＜1.2;-0.5＜δ＜0.5.Wherein working as the zirconium base electrolyte material is (Sc
2O
3)
x(ZrO
2)
1-x(0.001＜x＜1) composite cathode material (ScSZ) time is LSSM-ScSZ.When the zirconium base electrolyte material is (Y
2O
3)
x(ZrO
2)
1-x(0.001＜x＜1) composite cathode material (YSZ) time is LSSM-YSZ.
Material of the present invention can adopt sol-gel process to synthesize.Also can adopt solid reaction process, conventional methods such as coprecipitation are synthetic.Synthesize example with sol-gel process below and introduce preparation methods of the present invention.According to the chemical formula ratio of this material, take by weighing the Sc of stoichiometric proportion respectively
2O
3(analyzing pure) is dissolved in excessive HNO
3Add thermal agitation (14.5mol/L) and form Sc (NO
3)
3Solution dissolves the La (NO that the back adds stoichiometric proportion fully up to Sc
3)
3, Mn (CH
3COO)
2.4H
2O, and Sr (NO
3)
2(analyzing pure), again by metal population of ions: EDTA: the amount of citric acid (mol ratio)=1: 1: 2 takes by weighing EDTA and citric acid respectively, EDTA is dissolved in the ammoniacal liquor and stirs and pour in the nitrate solution for preparing after making it to dissolve fully, and then the pH value that adds citric acid 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 obtained presoma 250 ℃ of processing, at last with presoma at 600-1000 ℃ of roasting 1-10h, promptly get required (La
1-xSr
x)
a(Sc
yMn
1-y)
bO
3-δ(0.01＜x＜1,0.01＜y＜1,0.8＜a/b＜1.2).
Powder that this method is synthetic and ScSZ or YSZ powder are 1 according to mass ratio: ratio (5%-95%) is used high-energy ball milling (FRITSCH, Pulverisette 6) to grind and is made combination electrode material after 1h-10h fully mixes.
Make with ScZr (or YSZ) with platen press altogether and be the battery sheet of electrolytical anode-supported, anode be by 50%-100%NiO and 0-50%ScZr (or YSZ) mix by high-energy ball milling (FRITSCH, Pulverisette 6) and must.The electrolyte of anode-supported is calcined 5 hours down to form fine and close electrolytic thin-membrane at 1200-1500 ℃.Then the cathode powder that makes is blended in make in the organic solvent spray on the dielectric substrate after the cathode slurry after, 1000-1300 ℃ down calcining made the cathode layer of porous in 2 hours.
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.The flow of hydrogen is controlled by flow controller, and elargol is as current collector.
Beneficial effect:
1, cathode material of the present invention and zirconium base electrolyte material have compatibility preferably.
2, this material not only has high oxonium ion and electronic conduction ability, low thermal expansivity, and under the atmosphere of high temperature reduction, still have good chemistry and structural stability, show the very good material performance during especially for middle high temperature solid oxide fuel cell (SOFC) cathode material.
Description of drawings
Fig. 1 is the invention material La of institute
0.8Sr
0.2Sc
0.1Mn
0.9O
3-δWith La
0.8Sr
0.2MnO
3-δIn temperature is X-ray diffraction curve chart under 950 ℃.
Fig. 2 is the invention material La of institute
0.8Sr
0.2Sc
0.1Mn
0.9O
3-δWith La
0.8Sr
0.2MnO
3-δIn temperature is the further X-ray diffraction curve chart after handling half an hour under 800 ℃ the reducing atmosphere of moulding powder under 950 ℃.
Fig. 3 is the invention material La of institute
0.8Sr
0.2Sc
0.1Mn
0.9O
3-δBattery performance curve chart during as negative electrode.
Fig. 4 is the invention material La of institute
0.5Sr
0.5Sc
0.2Mn
0.8O
3-δWith La
0.5Sr
0.5MnO
3-δIn temperature is X-ray diffraction curve chart under 950 ℃.
Fig. 5 is the invention material La of institute
0.8Sr
0.2Sc
0.05Mn
0.95O
3-δWith La
0.8Sr
0.2MnO
3-δIn temperature is X-ray diffraction curve chart under 950 ℃.
Fig. 6 is the invention material La of institute
0.8Sr
0.2Sc
0.05Mn
0.95O
3-δBattery performance curve chart during as negative electrode.
Fig. 7 is the invention material La of institute
0.8Sr
0.2Sc
0.1Mn
0.9O
3-δX-ray diffraction curve chart with the YSZ composite cathode.
Fig. 8 is the invention material La of institute
0.8Sr
0.2Sc
0.1Mn
0.9O
3-δX-ray diffraction curve chart with the composite cathode of ScZr.
Embodiment
Embodiment one: the La of 0.05mol
0.8Sr
0.2Sc
0.1Mn
0.9O
3-δThe test of synthetic, structural stability and the performance test during as cell cathode.
Take by weighing the Sc of 0.34403g
2O
3(analyzing pure) is dissolved in the excessive HNO of 10ml
3Add thermal agitation (14.5mol/L) and form Sc (NO
3)
3Solution, dissolving back adding 88.18ml concentration fully up to Sc is the La (NO of 0.4536mol/ml
3)
3, the Mn (CH of 11.0295g
3COO)
2.4H
2O, and the Sr (NO of 2.1163g
3)
2(analyzing pure), again by metal population of ions: EDTA: the amount of citric acid (mol ratio)=1: 1: 2 takes by weighing EDTA29.225g and citric acid 42.028g respectively, EDTA is dissolved in the ammoniacal liquor of 80ml and stirs and pour in the nitrate solution for preparing after making it to dissolve fully, and then to add citric acid and come the pH value of regulator solution with ammoniacal liquor be 7, heating is stirred to and forms transparent colloidal sol, further colloidal sol is obtained presoma 250 ℃ of processing, at last with presoma at 850 ℃ of roasting 5h, promptly get required La
0.8Sr
0.2Sc
0.1Mn
0.9O
3-δThe XRD powder diffraction method is measured and is shown the perovskite structure that has formed pure phase, is illustrated in figure 1 as La
0.8Sr
0.2Sc
0.1Mn
0.9O
3-δWith La
0.8Sr
0.2MnO
3-δThe XRD phase structure, after the Sc that as can be seen from the figure mixes, still can form and La
0.8Sr
0.2MnO
3-δThe same perovskite structure.From the powder that makes, take by weighing 0.08g and pack in the U-shaped pipe, put into to be warming up to behind the tube furnace and feed 5% hydrogen treat after 800 ℃ after half an hour, measure with the XRD powder diffraction method after being cooled to room temperature rapidly, find that it still possesses perovskite structure preferably.And the La after handling under the same treatment condition
0.8Sr
0.2MnO
3-δThe perovskite structure of powder is then destroyed, as shown in Figure 2.
Making with ScZr with platen press altogether is the battery sheet of electrolytical anode-supported, anode be by 60%NiO and 40%ScZr mix by high-energy ball milling (FRITSCH, Pulverisette 6) and.The electrolyte of anode-supported is calcined 5 hours down to form fine and close electrolytic thin-membrane at 1400 ℃.Then with the La that makes
0.8Sr
0.2Sc
0.1Mn
0.9O
3-δPowder be blended in make in isopropyl alcohol and the glycerine spray on the dielectric substrate after the cathode slurry after, 1200 ℃ down calcining made the cathode layers of porous in 3 hours.
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.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 3, the open circuit voltage in the time of 850 ℃ reaches 1.08V, illustrates that the sealing of battery is better, power density reaches 920mW/cm
2, than the La under the same terms
0.8Sr
0.2MnO
3-δCathode material is higher than nearly one times.
Embodiment two: the La of 0.05mol
0.5Sr
0.5Sc
0.2Mn
0.8O
3-δSynthesizing of powder.
Take by weighing the Sc of 0.688g
2O
3(analyzing pure) is dissolved in the excessive HNO of 10ml
3Add thermal agitation (14.5mol/L) and form Sc (NO
3)
3Solution, dissolving back adding 55.11ml concentration fully up to Sc is the La (NO of 0.4536mol/ml
3)
3, the Mn (CH of 9.804g
3COO)
2.4H
2O, and the Sr (NO of 5.29g
3)
2(analyzing pure), again by metal population of ions: EDTA: the amount of citric acid (mol ratio)=1: 1: 2 takes by weighing EDTA29.225g and citric acid 42.028g respectively, EDTA is dissolved in the ammoniacal liquor of 80ml and stirs and pour in the nitrate solution for preparing after making it to dissolve fully, and then to add citric acid and come the pH value of regulator solution with ammoniacal liquor be 7, heating is stirred to and forms transparent colloidal sol, further colloidal sol is obtained presoma 250 ℃ of processing, at last with presoma at 850 ℃ of roasting 5h, promptly get required La
0.5Sr
0.5Sc
0.2Mn
0.8O
3-δThe XRD powder diffraction method is measured and to be shown the perovskite structure that has formed pure phase, and as shown in Figure 4, after the Sc that can find to mix from figure, peak value is obviously to the high angle skew, and this is that atomic radius owing to Sc causes greater than Mn.
Embodiment three: the La of 0.05mol
0.8Sr
0.2Sc
0.05Mn
0.95O
3-δThe synthetic and performance test during as cell cathode.
Take by weighing the Sc of 0.172g
2O
3(analyzing pure) is dissolved in the excessive HNO of 10ml
3Add thermal agitation (14.5mol/L) and form Sc (NO
3)
3Solution, dissolving back adding 88.18ml concentration fully up to Sc is the La (NO of 0.4536mol/ml
3)
3, the Mn (CH of 11.64g
3COO)
2.4H
2O, and the Sr (NO of 2.1163g
2)
2(analyzing pure), again by metal population of ions: EDTA: the amount of citric acid (mol ratio)=1: 1: 2 takes by weighing EDTA29.225g and citric acid 42.028g respectively, EDTA is dissolved in the ammoniacal liquor of 80ml and stirs and pour in the nitrate solution for preparing after making it to dissolve fully, and then to add citric acid and come the pH value of regulator solution with ammoniacal liquor be 7, heating is stirred to and forms transparent colloidal sol, further colloidal sol is obtained presoma 250 ℃ of processing, at last with presoma at 850 ℃ of roasting 5h, promptly get required La
0.5Sr
0.5Sc
0.0.05Mn
0.95O
3-δThe XRD powder diffraction method is measured and is shown the perovskite structure that has formed pure phase, as shown in Figure 5.
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.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 6, in the time of 850 ℃, with La
0.8Sr
0.2Sc
0.05Mn
0.95O
3-δPower density as the battery sheet of cathode material reaches 1350mW/cm
2, be higher than with La
0.8Sr
0.2Sc
0.1Mn
0.9O
3-δAs the battery sheet of cathode material, but La
0.8Sr
0.2Sc
0.05Mn
0.95O
3-δStability not as La
0.8Sr
0.2Sc
0.1Mn
0.9O
3-δSo, take all factors into consideration, or La
0.8Sr
0.2Sc
0.1Mn
0.9O
3-δBe the best.
Embodiment four: 0.05mol (Y
2O
3)
0.08(ZrO
2)
0.92And (Sc
2O
3)
0.1(ZrO
2)
0.9Synthetic and and the La of powder
0.8Sr
0.2Sc
0.1Mn
0.9O
3-δPowder is mixed with composite cathode.
Take by weighing Y (NO
3)
3.6H
2O3.064g and Zr (NO
3)
4.5H
2O19.75g (analyzing pure), again by metal ion: EDTA: the amount of citric acid (mol ratio)=1: 1: 2 takes by weighing EDTA 15.78g and citric acid 22.695g respectively, EDTA is dissolved in the ammoniacal liquor of 40ml and stirs and pour in the nitrate solution for preparing after making it to dissolve fully, and then the pH value to 7 that adds citric acid and come regulator solution with ammoniacal liquor, heating is stirred to and forms transparent colloidal sol, further colloidal sol is obtained presoma 250 ℃ of processing, at last with presoma at 750 ℃ of roasting 5h, promptly get required YSZ.Take by weighing prepared La among prepared YSZ powder of 1g and the 1g embodiment one
0.8Sr
0.2Sc
0.1Mn
0.9O
3-δMake composite cathode (LSSM+YSZ) after in high-energy ball milling, fully grinding 2h.The XRD powder diffraction method is measured figure as shown in Figure 7.
Take by weighing Sc
2O
30.688g be dissolved in excessive HNO
3Add thermal agitation (14.5mol/L) and form Sc (NO
2)
3Solution dissolves the back fully up to Sc and adds Zr (NO
3)
4.5H
2O 19.32g (analyzing pure), again by metal ion: EDTA: the amount of citric acid (mol ratio)=1: 1: 2 takes by weighing EDTA 16.074g and citric acid 23.12g respectively, EDTA is dissolved in the ammoniacal liquor of 50ml and stirs and pour in the nitrate solution for preparing after making it to dissolve fully, and then the pH value to 7 that adds citric acid and come regulator solution with ammoniacal liquor, heating is stirred to and forms transparent colloidal sol, further colloidal sol is obtained presoma 250 ℃ of processing, at last with presoma at 750 ℃ of roasting 5h, promptly get required ScZr.Take by weighing prepared La among prepared ScZr powder of 1g and the 1g embodiment one
0.8Sr
0.2Sc
0.1Mn
0.9O
3-δMake composite cathode (LSSM+ScZr) after in high-energy ball milling, fully grinding 2h.The XRD powder diffraction method is measured figure as shown in Figure 8.
Claims (6)
1. the cathode material of middle high temperature solid oxide fuel cell is characterized in that its molecular formula is (La
1-xSr
x)
a(Sc
yMn
1-y)
bO
3-δ, cathode material, 0.01＜x＜1,0.01＜y＜1,0.8＜a/b＜1.2 wherein;-0.5＜δ＜0.5.
2. cathode material according to claim 1 is characterized in that its molecular formula is La
0.8Sr
0.2Sc
0.05Mn
0.95O
3-δ, wherein-0.5＜δ＜0.5.
3. a composite cathode material that contains the described material of claim 1 is characterized in that composite cathode material is to be (La by molecular formula
1-xSr
x)
a(Sc
yMn
1-y)
bO
3-δ(LSSM) composite material of, cathode material and zirconium base electrolyte material, wherein 0.01＜x＜1,0.01＜y＜1,0.8＜a/b＜1.2;-0.5＜δ＜0.5.
4. composite cathode material according to claim 3 is characterized in that described zirconium base electrolyte material is (Sc
2O
3)
x(ZrO
2)
1-x(0.001＜x＜1), composite cathode material are LSSM-ScSZ.
5. composite cathode material according to claim 3 is characterized in that described zirconium base electrolyte material is (Y
2O
3)
x(ZrO
2)
1-x(0.001＜x＜1), composite cathode material are LSSM-YSZ.
6. cathode material according to claim 1 is characterized in that adopting sol-gel process, solid reaction process or coprecipitation synthetic.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100218054A CN100517840C (en) | 2007-04-29 | 2007-04-29 | medium-high temperature solid oxide fuel cell cathode material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102340008A (en) * | 2010-07-22 | 2012-02-01 | 中国科学院大连化学物理研究所 | Cathode material of solid oxide fuel cell and preparation method thereof |
| DE102012221427A1 (en) | 2011-11-30 | 2013-06-06 | Robert Bosch Gmbh | Fuel cell system i.e. high temperature-fuel cell system, for use in e.g. vehicle, has fuel cells connected in series and/or parallel by interconnectors, where part of interconnectors is made from material with perovskite structure |
| CN105576251A (en) * | 2016-02-03 | 2016-05-11 | 上海交通大学 | SSOFC electrode material and composite electrode material thereof |
| CN109244536A (en) * | 2018-09-21 | 2019-01-18 | 佛山皖和新能源科技有限公司 | A kind of preparation method of densification isotypy composite solid electrolyte material |
| CN112670525A (en) * | 2020-12-01 | 2021-04-16 | 全球能源互联网研究院有限公司 | Solid oxide fuel cell electrode material |
| CN118271088A (en) * | 2024-05-31 | 2024-07-02 | 西南石油大学 | Bismuth-doped intermediate-temperature SOFC cathode material and preparation method and application thereof |
-
2007
- 2007-04-29 CN CNB2007100218054A patent/CN100517840C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102340008A (en) * | 2010-07-22 | 2012-02-01 | 中国科学院大连化学物理研究所 | Cathode material of solid oxide fuel cell and preparation method thereof |
| DE102012221427A1 (en) | 2011-11-30 | 2013-06-06 | Robert Bosch Gmbh | Fuel cell system i.e. high temperature-fuel cell system, for use in e.g. vehicle, has fuel cells connected in series and/or parallel by interconnectors, where part of interconnectors is made from material with perovskite structure |
| CN105576251A (en) * | 2016-02-03 | 2016-05-11 | 上海交通大学 | SSOFC electrode material and composite electrode material thereof |
| CN109244536A (en) * | 2018-09-21 | 2019-01-18 | 佛山皖和新能源科技有限公司 | A kind of preparation method of densification isotypy composite solid electrolyte material |
| CN109244536B (en) * | 2018-09-21 | 2020-04-24 | 深圳凯泽鑫电子有限公司 | Preparation method of compact and uniform solid composite electrolyte material |
| CN112670525A (en) * | 2020-12-01 | 2021-04-16 | 全球能源互联网研究院有限公司 | Solid oxide fuel cell electrode material |
| CN112670525B (en) * | 2020-12-01 | 2022-11-25 | 全球能源互联网研究院有限公司 | Solid oxide fuel cell electrode material |
| CN118271088A (en) * | 2024-05-31 | 2024-07-02 | 西南石油大学 | Bismuth-doped intermediate-temperature SOFC cathode material and preparation method and application thereof |
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| CN100517840C (en) | 2009-07-22 |
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