CN102054991B - Cathode material of solid oxide fuel cell and preparation method thereof - Google Patents
Cathode material of solid oxide fuel cell and preparation method thereof Download PDFInfo
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- CN102054991B CN102054991B CN2010105625468A CN201010562546A CN102054991B CN 102054991 B CN102054991 B CN 102054991B CN 2010105625468 A CN2010105625468 A CN 2010105625468A CN 201010562546 A CN201010562546 A CN 201010562546A CN 102054991 B CN102054991 B CN 102054991B
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- fuel cell
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- glycine
- oxide fuel
- powder
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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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Abstract
The invention belongs to the field of fuel cells, in particular the field of a cathode material of a solid oxide fuel cell. The cathode material of the solid oxide fuel cell has a molecular formula of LaxSr2-xFeO4+/-delta, and is characterized in that: x is equal to 1.2; and the molecular formula is La1.2Sr0.8FeO4+/-delta. The invention also discloses a method for preparing the cathode material. Compared with the prior art, a glycine method provided by the invention for preparing the cathode material of the solid oxide fuel cell has the advantages that: 1, compared with a solid-state reaction method, the glycine method has short preparation period and low thermal treatment temperature of powder, and the obtained powder is purer and can be produced on a large scale; 2, compared with a citric acid-nitrate method and an ethylene diamine tetraacetic acid (EDTA)-citric acid method, the glycine method has a simple preparation process and the pH value of solution is not required to be adjusted; and 3, the glycine is used as an oxidant, so the reaction is quickened and smaller particle diameter can be obtained.
Description
Technical field
The invention belongs to fuel cell field, specifically the cathode material for solid-oxide fuel cell field.
Background technology
Fuel cell is the device that a kind of chemical energy with fuel changes into electric energy, is not subjected to the restriction of Carnot cycle, has energy transformation ratio height (can reach 85%), environmental friendliness (i.e. very low NO
x, SO
2The characteristics such as the discharge capacity of discharging and noise emissions), hardly nitrogen oxide and oxysulfide, carbon dioxide also reduces more than 40% than the power plant of routine, except this, builds fuel cell power plant, has the time of founding the factory weak point, and floor space is little.Therefore, it is a kind of tool future, clean generation technology, is called as the green energy resource of 21 century.Solid Oxide Fuel Cell (SOFC) is except the characteristics with fuel cell, and itself also has the environment structure of whole solid state, fuel range is wide, working temperature is high, comprehensive utilization ratio high and being widely used.
At present, the operating temperature that reduces SOFC is study hotspot these years, yet along with the reduction of operating temperature, Ohmic resistance and the polarization resistance of Solid Oxide Fuel Cell increase greatly, thereby have reduced the efficient of battery.One of path that addresses these problems is exactly to seek suitable electrode material, and these electrode materials and electrolyte are complementary and the electro-chemical activity height, thereby reduces the polarization resistance of battery, is fit to battery and works under middle low temperature.
The research of intermediate temperature SOFC novel cathode material mainly concentrates on ABO
3On type perovskite structure electronics-oxonium ion mixed conductor.Wherein, La
1-xSr
xCo
1-yFe
yO
3(LSCF) system the most people pay attention to.Under 800 ℃, the electronic conductivity of LSCF system reaches 10
2～10
3S/cm, oxonium ion can reach 10 by the conduction of oxygen room flooding mechanism
-2The oxygen ionic conductivity of～100S/cm (Beson S J, Waller D, Kilner J A), still, the thermal coefficient of expansion of LSFO system is high, is not inconsistent with LSGM electrolyte thermal matching.A
2B0
4+ δThe type mixed conductor has suitable thermal coefficient of expansion ((10.5～14.2) * 10
-6K
-1), can be preferably with LSGM in warm electrolyte be complementary La especially
2NiO
4The base cathode material becomes study hotspot in recent years, La
2NiO
4+ δConductive characteristic is that (300～500 ℃) occur by the transformation of semi-conductor type conduction to the metal mold conduction at a lower temperature, and the peak of total conductivity appears at lower temperature range, (Kharton V V, Viskup AP, Kovalevsky AV).Most study is to replace La at the A bit position now, provides more oxygen room to improve the performance of material.There is researcher (A.J.Jennings, C.K.M.Shaw, S.J.Skinner) to adopt solid state reaction to prepare La
xSr
2-xFeO
4+ δ, conductivity, thermal stability and the architectural feature of material have been studied in x=0.1～1 wherein, think La
xSr
2-xFeO
4+ δIt is a kind of potential cathode material for solid-oxide fuel cell.
Summary of the invention
Purpose of the present invention mainly is to replace the Ni position with Fe, partly substitutes the La position with Sr, has studied La
2NiO
4The A bit position of sill replaces, after the B position replaces on the impact of the electric conductivity of material.The present invention adopts powders by glycine-nitrate process to prepare La
xSr
2-xFeO
4 ± δ(x=1.2).
A kind of cathode material for solid-oxide fuel cell of the present invention, molecular formula are La
xSr
2-xFeO
4 ± δ, it is characterized in that: x=1.2, molecular formula is La
1.2Sr
0.8FeO
4 ± δ
A kind of preparation method of cathode material for solid-oxide fuel cell is characterized in that, described step is as follows:
(1) according to La
1.2Sr
0.8FeO
4 ± δStoichiometric proportion takes by weighing respectively lanthanum nitrate, strontium nitrate, Fe(NO3)39H2O raw material, is 1.7～2.2 according to the ratio of glycine and metal ion, takes by weighing glycine, it is dissolved in the deionized water, and ultrasonic being uniformly dispersed, form transparent solution;
(2) above-mentioned clear solution is mixed, stir, be heated to 200～250 ℃ in evaporating dish, the moisture that evaporate to dryness is unnecessary is until spontaneous combustion forms porous foam shape powder;
(3) the foam-like powder is ground, after 500 ℃～700 ℃ preliminary treatment, grind, 800～1000 ℃ of calcination obtain required powder;
(4) with after 500 ℃～700 ℃ preliminary treatment of foam-like powder, grind, join in the mould, be under 25MPa～30MPa in gauge pressure, behind pressurize 25min～40min, the strip sample that the demoulding forms, behind 800 ℃～1000 ℃ calcination 7～9h, 1400 ℃～1500 ℃ sintering 10～14h in high temperature furnace obtain fine and close ceramic body again, namely obtain density cathode material for solid-oxide fuel cell La
1.2Sr
0.8FeO
4 ± δBlock materials.
Compared with prior art, glycine method provided by the present invention prepares cathode material for solid-oxide fuel cell and has the following advantages:
1. compare with solid state reaction, the glycine method manufacturing cycle is short, and the heat treatment temperature of powder is low, and the powder that obtains is compared pure, can produce in enormous quantities.
2. compare with the EDTA-citric acid method with citric acid-nitrate method, the technique of glycine method preparation is simple, does not need the pH value of solution is regulated.
3. oxidant is selected glycine, adds the speed of fast response, can obtain less particle diameter.
Description of drawings
Fig. 1 is preparation method's flow chart of the present invention.
Fig. 2 is that the present invention adopts the synthetic La of glycine
1.2Sr
0.8FeO
4 ± δX ray diffracting spectrum.
Fig. 3 is that the present invention adopts the synthetic La of glycine method
1.2Sr
0.8FeO
4 ± δThe high-resolution-ration transmission electric-lens photo of powder, average grain size are about 150nm.
Fig. 4 is La
1.2Sr
0.8FeO
4 ± δConductivity at 300 ℃～900 ℃ varies with temperature graph of a relation.
Embodiment
Below in conjunction with object lesson technical scheme of the present invention is described:
Embodiment 1:0.04mol La
1.2Sr
0.8FeO
4 ± δThe synthetic and conductivity test of glycine method
1. the lanthanum nitrate of weighing 0.048mol adds deionized water in beaker, is placed on the electric furnace and heats 200 ℃, stirs, and dissolving forms colourless transparent solution.
2. the strontium nitrate of weighing 0.032mol is put into beaker, adds deionized water, and ultrasonic dispersion is dissolved it fully.
3. the Fe(NO3)39H2O of weighing 0.04mol adds the ultrasonic dispersion of deionized water it is dissolved fully
4. the glycine of weighing 0.24mol adds the ultrasonic dispersion of deionized water it is dissolved fully.
5. above-mentioned clear solution is mixed, be heated to 230 ℃ in evaporating dish, the moisture that evaporate to dryness is unnecessary is until spontaneous combustion forms porous foam shape powder.
With the foam-like powder after 600 ℃ of preliminary treatment, grind, take out a part of powder at 900 ℃ of calcination 8h, cool to room temperature grinds, and does the X-ray diffraction test.
7. the powder after 600 ℃ of preliminary treatment being ground, join in the mould, is under the 28MPa in gauge pressure, behind the pressurize 30min, and the strip sample that the demoulding forms, behind 900 ℃ of calcination 8h, 1450 ℃ of sintering 12h in high temperature furnace obtain fine and close ceramic body again.
8. utilize DC four point probe method that the ceramic body of densification is carried out the conductivity test, Range of measuring temp: 300 ℃～900 ℃, test atmosphere is air atmosphere.
Embodiment 2:0.08mol La
1.2Sr
0.8FeO
4 ± δThe synthetic and conductivity test of glycine method
1. according to La
1.2Sr
0.8FeO
4 ± δThe stoichiometric proportion of material, the Fe(NO3)39H2O of the lanthanum nitrate of weighing 0.096mol, the strontium nitrate of 0.064mol, 0.08mol is dissolved in deionized water, and dissolving forms colourless transparent solution.
2. be 1.8 according to glycine with the metal ion ratio, the glycine of weighing 0.432mol adds the ultrasonic dispersion of deionized water it is dissolved fully.
3. above-mentioned clear solution is mixed, stirring also is heated to 200 ℃ in evaporating dish, and the moisture that evaporate to dryness is unnecessary is until spontaneous combustion forms porous foam shape powder.
With the foam-like powder after 500 ℃ of preliminary treatment, grind, take out a part of powder at 950 ℃ of calcination 10b, cool to room temperature grinds, and does the X-ray diffraction test.
5. the powder after 500 ℃ of preliminary treatment being ground, join in the mould, is under the 25MPa in gauge pressure, behind the pressurize 25min, and the strip sample that the demoulding forms, behind 950 ℃ of calcination 10h, 1500 ℃ of sintering 10h in high temperature furnace obtain fine and close ceramic body again.
6. utilize DC four point probe method that the ceramic body of densification is carried out the conductivity test, Range of measuring temp: 300 ℃～900 ℃, test atmosphere is air atmosphere.
Embodiment 3:0.02mol La
1.2Sr
0.8FeO
4 ± δThe synthetic and conductivity test of glycine method
1. according to La
1.2Sr
0.8FeO
4 ± δThe stoichiometric proportion of metal ion, the Fe(NO3)39H2O of the lanthanum nitrate of weighing 0.024mol, the strontium nitrate of 0.016mol, 0.02mol, ratio according to glycine and metal ion is 2.2, and the glycine of weighing 0.132mol dissolves in deionized water, ultrasonic dispersion is dissolved it fully, form colourless transparent solution, in evaporating dish, be heated to 250 ℃, the moisture that evaporate to dryness is unnecessary, until spontaneous combustion forms porous foam shape powder.
With the foam-like powder 650 ℃ of preliminary treatment, grind, take out a part of powder at 1000 ℃ of calcination 8h, cool to room temperature grinds, and does the X-ray diffraction test.
3. the powder after 650 ℃ of preliminary treatment being ground, join in the mould, is under the 30MPa in gauge pressure, behind the pressurize 35min, and the strip sample that the demoulding forms, behind 1000 ℃ of calcination 8h, 1400 ℃ of sintering 14h in high temperature furnace obtain fine and close ceramic body again.
4. utilize DC four point probe method that the ceramic body of densification is carried out the conductivity test, Range of measuring temp: 300 ℃～900 ℃, test atmosphere is air atmosphere.
Claims (1)
1. the preparation method of a cathode material for solid-oxide fuel cell is characterized in that, step is as follows:
(1) according to La
1.2Sr
0.8FeO
4 ± δStoichiometric proportion takes by weighing respectively lanthanum nitrate, strontium nitrate, Fe(NO3)39H2O raw material, is 1.7～2.2 according to the ratio of glycine and metal ion, takes by weighing glycine, it is dissolved in the deionized water, and ultrasonic being uniformly dispersed, form transparent solution;
(2) above-mentioned clear solution is mixed, stir, be heated to 200～250 ℃ in evaporating dish, the moisture that evaporate to dryness is unnecessary is until spontaneous combustion forms porous foam shape powder;
(3) with after 500 ℃～700 ℃ preliminary treatment of foam-like powder, grind, join in the mould, be under 25MPa～30MPa in gauge pressure, behind pressurize 25min～40min, the strip sample that the demoulding forms, behind 800 ℃～1000 ℃ calcination 7～9h, 1400 ℃～1500 ℃ sintering 10～14h in high temperature furnace obtain fine and close ceramic body again, namely obtain fine and close cathode material for solid-oxide fuel cell La
1.2Sr
0.8FeO
4 ± δBlock materials.
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|---|---|---|---|
| CN2010105625468A CN102054991B (en) | 2010-11-23 | 2010-11-23 | Cathode material of solid oxide fuel cell and preparation method thereof |
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|---|---|---|---|
| CN2010105625468A CN102054991B (en) | 2010-11-23 | 2010-11-23 | Cathode material of solid oxide fuel cell and preparation method thereof |
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| CN102054991A CN102054991A (en) | 2011-05-11 |
| CN102054991B true CN102054991B (en) | 2013-01-30 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103789876B (en) * | 2014-01-24 | 2016-02-10 | 山西师范大学 | The synthetic method of banded porous cadmium ferrite nanofiber |
| CN104916850B (en) * | 2015-04-27 | 2017-06-06 | 上海邦民新能源科技有限公司 | Cathode of solid oxide fuel cell material and have its composite cathode material and preparation method thereof and battery composite cathode preparation method |
| CN111129517A (en) * | 2019-12-30 | 2020-05-08 | 黑龙江大学 | Preparation method of Ruddlesden-Popper layered structure iron-based cathode catalyst |
| CN112687886B (en) * | 2020-12-22 | 2022-07-05 | 上海应用技术大学 | Intermediate-temperature solid oxide fuel cell composite cathode and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101000965A (en) * | 2006-12-22 | 2007-07-18 | 清华大学 | Anode-electrolyte-cathode assembly of middly temp SOFC and preparation method thereof |
| CN101572315A (en) * | 2009-06-05 | 2009-11-04 | 黑龙江大学 | Method for preparing catelectrode material Ln<2-x>A'<x>CuO<4+/-delta> with K2NiF4 structure by electrostatic spinning |
-
2010
- 2010-11-23 CN CN2010105625468A patent/CN102054991B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101000965A (en) * | 2006-12-22 | 2007-07-18 | 清华大学 | Anode-electrolyte-cathode assembly of middly temp SOFC and preparation method thereof |
| CN101572315A (en) * | 2009-06-05 | 2009-11-04 | 黑龙江大学 | Method for preparing catelectrode material Ln<2-x>A'<x>CuO<4+/-delta> with K2NiF4 structure by electrostatic spinning |
Non-Patent Citations (1)
| Title |
|---|
| A.J. Jennings, S.J. Skinner.Thermal stability and conduction properties of the LaxSr2-xFeO4+δsystem.《Solid State Ionics》.2002,第663-667页. * |
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