CN102569786A - Perovskite Co-based composite negative electrode material as well as preparation and application thereof - Google Patents
Perovskite Co-based composite negative electrode material as well as preparation and application thereof Download PDFInfo
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- CN102569786A CN102569786A CN2012100176387A CN201210017638A CN102569786A CN 102569786 A CN102569786 A CN 102569786A CN 2012100176387 A CN2012100176387 A CN 2012100176387A CN 201210017638 A CN201210017638 A CN 201210017638A CN 102569786 A CN102569786 A CN 102569786A
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- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000007773 negative electrode material Substances 0.000 title abstract 5
- 239000000446 fuel Substances 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims description 63
- 239000010406 cathode material Substances 0.000 claims description 31
- 239000003792 electrolyte Substances 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 13
- 229910002437 Ce0.8Sm0.2O2−δ Inorganic materials 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 239000000565 sealant Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims 2
- 239000002243 precursor Substances 0.000 claims 2
- 229910052684 Cerium Inorganic materials 0.000 abstract description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract 2
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 abstract 1
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract 1
- 235000017550 sodium carbonate Nutrition 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 42
- 239000011259 mixed solution Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 229910002651 NO3 Inorganic materials 0.000 description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000011533 mixed conductor Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910052772 Samarium Inorganic materials 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 238000005485 electric heating Methods 0.000 description 4
- 239000010416 ion conductor Substances 0.000 description 4
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- RQBNZBBFGYBCPH-UHFFFAOYSA-N [Sm]=O Chemical compound [Sm]=O RQBNZBBFGYBCPH-UHFFFAOYSA-N 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 239000010436 fluorite Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 241000143437 Aciculosporium take Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 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 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 description 1
- -1 oxonium ion Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 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
-
- 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
The invention relates to an A-site double-doped Co-based perovskite composite negative electrode material as well as preparation and application thereof, and relates to the field of an intermediate-temperature solid oxide fuel cell, belonging to the field of new energy materials. The perovskite Co-based composite negative electrode material consists of the following components in percentage by mass: 50% of La0.7Sr0.15Ca0.15Co0.8Fe0.2O(3-delta), 37.5% of Ce0.8Sm0.2O(2-delta) and 12.5% of Li2CO3 and Na2CO3. The composite negative electrode material has high electronic and ionic conductivities, relatively high intermediate-temperature catalytic activity and good electrochemical performance, and is relatively well compatible with a cerium-based electrolytic material in terms of thermal performance and chemical performance; and moreover, as the negative electrode of a intermediate-temperature solid oxide fuel cell, the composite negative electrode material has relatively high output power.
Description
Technical field
The present invention relates to a kind of A position codope Co based perovskite type composite cathode material and preparation and application, relate to the intermediate temperature solid oxide fuel cell field, belong to the new energy materials field.
Background technology
SOFC (SOFC; Solid oxide fuel cell) is a kind of energy conversion device that directly chemical energy of fuel gas and oxidizing gas is converted to the total solids assembly of electric energy; Have clean and efficient advantage, thereby be known as the green energy resource of 21st century.
At present, traditional cathode material lanthanum manganate is under the condition of middle temperature, promptly below 800 ℃; Conductivity reduces rapidly; Polarization resistance increases rapidly, is difficult to satisfy the requirement of intermediate temperature solid oxide fuel cell (ITSOFC, Intermediate temperature solid oxide fuel cell).One of path that addresses these problems is exactly to seek suitable electrode material, requires these electrode materials and electrolyte to be complementary and the electro-chemical activity height, thereby reduces the polarization resistance of battery, is fit to battery and under middle low temperature, works.
The research of ITSOFC novel cathode material mainly concentrates on ABO
3On type perovskite structure electronics-cation 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 through the conduction of oxygen room flooding mechanism
-2The oxygen ionic conductivity of～100S/cm, but the thermal coefficient of expansion of LSCF system is high, with CeO
2The hot matching of base electrolyte is not inconsistent, and single doping Ca
2+La
1-xCa
xCo
1-yFe
yO
3The cathode material thermal coefficient of expansion is lower, and electrical property is relatively poor.
Summary of the invention
The purpose of this invention is to provide a kind of Ca-Ti ore type Co base composite cathode material, this cathode material is made up of oxygen ion conductor, proton conductor, electronics-oxonium ion mixed conductor.Oxygen ion conductor is the cerium base oxide with samarium doping of fluorite structure, and proton conductor is a carbonate, and wherein the mixture of the cerium base oxide of samarium doping and carbonate forms oxonium ion-proton mixed conductor.
The technical scheme that the present invention deals with problems is a kind of Ca-Ti ore type Co base composite cathode material, by mass percentage, is made up of following component:
La
0.7Sr
0.15Ca
0.15Co
0.8Fe
0.2O
3-δ 50％
Ce
0.8Sm
0.2O
2-δ 37.5％
Li
2CO
3And Na
2CO
3The mixture of forming in 2: 1 in molar ratio 12.5%
Another object of the present invention provides the preparation method of above-mentioned Ca-Ti ore type Co base composite cathode material, and it comprises La
0.7Sr
0.15Ca
0.15Co
0.8Fe
0.2O
3-δ, Ce
0.8Sm
0.2O
2-δAnd the preparation of Ca-Ti ore type Co base composite cathode material.
1. electronics-oxonium ion mixed conductor La
0.7Sr
0.15Ca
0.15Co
0.8Fe
0.2O
3-δThe cathode material preparation:
A. with La (NO
3)
36H
2O, Sr (NO
3)
2, Ca (NO
3)
24H
2O, Co (NO
3)
36H
2O and Fe (NO
3)
39H
2O presses La
0.7Sr
0.15Ca
0.15Co
0.8Fe
0.2O
3-δThe stoichiometric proportion weighing after, use dissolved in distilled water, form nitrate mixed solution; According to metal ion mol ratio in citric acid and the nitrate mixed solution is to take by weighing citric acid at 1.5～2: 1, uses the dissolved in distilled water citric acid;
B. citric acid solution is poured in the nitrate mixed solution, using ammoniacal liquor to regulate pH is 2;
C. step b is obtained mixed solution and stir, until forming gel at 65～75 ℃ of lower magnetic forces; Place the electric heating constant temperature air dry oven to make presoma gel in 120 ℃ of dryings;
D. with synthetic presoma at 900 ℃～1000 ℃ microwave calcination 1.5～2h.
2. oxygen ion conductor Ce
0.8Sm
0.2O
2-δPreparation:
A. press Ce
0.8Sm
0.2O
2-δThe stoichiometric proportion raw materials weighing, with red fuming nitric acid (RFNA) dissolved oxygen samarium, with dissolved in distilled water cerous nitrate and citric acid;
B. samarium nitrate solution is poured in the cerous nitrate solution, again citric acid is poured in the nitrate mixed solution, regulate pH value to 8 with ammoniacal liquor;
C. mixed solution is stirred at 65～75 ℃ of lower magnetic forces, until forming gel; Gel is placed the electric heating constant temperature air dry oven, and dry 2h makes presoma under 120 ℃;
D. with synthetic presoma at 900 ℃～1000 ℃ microwave calcination 1.5～2h, promptly get samarium doped cerium oxide (SDC, samarium doped ceria) electrolyte powder.
3. Ca-Ti ore type Co base composite cathode material preparation:
A. take by weighing Li by 1/3rd of SDC electrolyte powder quality
2CO
3And Na
2CO
3Powder, wherein Li
2CO
3With Na
2CO
3Mol ratio be 2: 1, behind SDC powder and the carbonate mixed grinding at 650 ℃ of following microwave calcination 0.5h, make SDC and carbonate composite electrolyte powder (CSC, ceria-salt-composite);
B. with La
0.7Sr
0.15Ca
0.15Co
0.8Fe
0.2O
3-δPowder and CSC composite electrolyte powder mixed grinding after make Ca-Ti ore type Co base composite cathode material with mass ratio at 1: 1.
Another purpose of the present invention provides a kind of intermediate temperature solid oxide fuel cell, and this fuel cell is a cathode material with Ca-Ti ore type Co based composites, and the preparation method is following:
A. by Li: Cu: the Ni mol ratio is to take by weighing Li at 1: 4: 5
2CO
3, CuO and NiO powder, at 650 ℃ of following microwave calcination 0.5h, make Li behind the mixed grinding
2CO
3-CuO-NiO (LCN) anode powder;
B. be anode material with LCN powder and CSC composite electrolyte powder with 1: 1 mixed grinding of mass ratio; With CSC powder or SDC powder as electrolyte; Ca-Ti ore type Co base composite cathode material is a negative electrode; In mould, successively place anode powder, electrolyte powder, cathode powder, monocell is taked the form of anode-supported, in the moulding of 200MPa pressed.
C. the effective active area 0.64cm of monocell
2, monocell is packed in the anchor clamps, adopt the silver slurry to be sealant.
D. battery is fuel with hydrogen, and air is an oxidant, and gas flow rate is 80～120mL/min.
The invention has the beneficial effects as follows: A disclosed by the invention position codope Ca-Ti ore type Co base composite cathode material not only has high electronics, ionic conductivity, also has higher middle temperature catalytic activity and excellent electrochemical properties.With the cerium base electrolyte material having compatibility preferably aspect hot property and the chemical property, as the negative electrode of middle temperature solid oxidized fuel cell, have higher power output.
Description of drawings
Accompanying drawing of the present invention is 2 width of cloth,
The La of Fig. 1 embodiment 1
0.7Sr
0.15Ca
0.15Co
0.8Fe
0.2O
3-δThe XRD spectra of powder;
The SDC powder of Fig. 2 embodiment 1 and the XRD spectra of CSC powder.
Embodiment
Following non-limiting example can make those of ordinary skill in the art more fully understand the present invention, but does not limit the present invention in any way.
Embodiment 1
1. electronics-oxonium ion mixed conductor La
0.7Sr
0.15Ca
0.15Co
0.8Fe
0.2O
3-δThe cathode material preparation
A. with La (NO
3)
36H
2O (AR), Sr (NO
3)
2(AR), Ca (NO
3)
24H
2O (AR), Co (NO
3)
36H
2O (AR) and Fe (NO
3)
39H
2O (AR) presses La
0.7Sr
0.15Ca
0.15Co
0.8Fe
0.2O
3-δThe stoichiometric proportion weighing after, use dissolved in distilled water, form nitrate mixed solution; According to the mol ratio of citric acid (AR) and metal ion is to take by weighing citric acid at 1.5: 1, uses the dissolved in distilled water citric acid;
B. citric acid solution is poured in the nitrate mixed solution, using ammoniacal liquor to regulate pH is 2;
C. mixed solution is stirred at 65～75 ℃ of lower magnetic forces, along with the continuous evaporation of solvent, solution retrogradation gradually forms gel at last; Place the electric heating constant temperature air dry oven to make presoma gel in 120 ℃ of dryings;
D. with presoma at 900 ℃ of following microwave calcination 2h, make the electronics-oxonium ion mixed conductor La of perovskite structure
0.7Sr
0.15Ca
0.15Co
0.8Fe
0.2O
3-δCathode material.
Fig. 1 is the La of preparation
0.7Sr
0.15Ca
0.15Co
0.8Fe
0.2O
3-δThe XRD spectra of powder can determine that it is perovskite structure according to collection of illustrative plates.
2. oxygen ion conductor Ce
0.8Sm
0.2O
2-δPreparation
A. press Ce
0.8Sm
0.2O
2-δThe stoichiometric proportion raw materials weighing, use dense HNO
3(>=99.5%) dissolved oxygen samarium (>=99.0%) is with dissolved in distilled water cerous nitrate (>=99.0%) and citric acid (AR);
B. samarium nitrate solution is poured in the cerous nitrate solution, again citric acid is poured in the nitrate mixed solution, regulate pH value to 8 with ammoniacal liquor;
C. mixed solution is stirred at 65～75 ℃ of lower magnetic forces, until forming gel; Gel is placed the electric heating constant temperature air dry oven, and dry 2h makes presoma under 120 ℃;
D. with presoma at 900 ℃ of following microwave calcination 1.5h, make SDC electrolyte powder.
Fig. 2 is the XRD spectra of SDC powder and CSC powder, and wherein the collection of illustrative plates according to the SDC powder is a fluorite type structure.
3. Ca-Ti ore type Co base composite cathode material preparation
A. at first take by weighing Li with 1/3rd of SDC electrolyte powder quality
2CO
3(produce in the Hunan,>=96.0%) and Na
2CO
3(produce in Beijing,>=99.8%) powder, wherein Li
2CO
3With Na
2CO
3Mol ratio be 2: 1.At 650 ℃ of following microwave calcination 0.5h, make CSC (CSC, ceria-salt-composite) compound electrolyte material behind SDC powder and the carbonate mixed grinding;
B. with La
0.7Sr
0.15Ca
0.15Co
0.8Fe
0.2O
3-δMixed grinding after make Ca-Ti ore type Co base composite cathode material with CSC composite electrolyte powder at 1: 1 with mass ratio.
Fig. 2 is the XRD spectra of SDC powder and CSC powder.As shown in the figure, the collection of illustrative plates of SDC powder and CSC powder shows that it is fluorite type structure, SDC powder and carbonate mixed calcining are described after, do not generate new component.
4. SOFC preparation
A. with Li: Cu: the Ni mol ratio takes by weighing Li at 1: 4: 5
2CO
3, CuO (>=99.0%) and NiO (>=99.0%) powder, at 650 ℃ of following microwave calcination 0.5h, make LCN anode powder behind the mixed grinding.
B.LCN powder and CSC composite electrolyte powder are anode with 1: 1 mixed grinding of mass ratio, are dielectric substrate with the CSC powder, and prepared Ca-Ti ore type Co base composite cathode material is a negative electrode; In mould, successively place anode powder, electrolyte powder, cathode powder, monocell is taked the form of anode-supported, in the moulding of 200MPa pressed.
C. the effective active area 0.64cm of monocell
2, monocell is packed in the anchor clamps, adopt the silver slurry to be sealant.
D. battery is fuel with hydrogen, and air is an oxidant, and gas flow rate is 80～120mL/min.
The voltage and current of difference test battery two interpolars in 500 ℃～650 ℃ temperature ranges, the maximum power density of gained battery is 584.1mW/cm at 650 ℃
2
Embodiment 2
1. electronics-oxonium ion mixed conductor La
0.7Sr
0.15Ca
0.15Co
0.8Fe
0.2O
3-δCathode material is synthetic
A. with La (NO
3)
36H
2O, Sr (NO
3)
2, Ca (NO
3)
24H
2O, Co (NO
3)
36H
2O and Fe (NO
3)
39H
2O presses La
0.7Sr
0.15Ca
0.15Co
0.8Fe
0.2O
3-δAfter the stoichiometric proportion weighing, use dissolved in distilled water, form nitrate mixed solution; According to the mol ratio of metal ion in citric acid and the nitrate mixed solution is to take by weighing citric acid at 2: 1, uses the dissolved in distilled water citric acid.
B. with embodiment 1.
C. with embodiment 1.
D. with presoma at 1000 ℃ of following microwave calcination 1.5h, make the electronics-oxonium ion mixed conductor La of perovskite structure
0.7Sr
0.15Ca
0.15Co
0.8Fe
0.2O
3-δCathode material.
Step is 2. with 3. with embodiment 1;
Wherein 4. the b step is following, and other steps are with embodiment 1:
B.LCN powder and CSC composite electrolyte powder are anode with 1: 1 mixed grinding of mass ratio, are dielectric substrate with the SDC powder, and prepared Ca-Ti ore type Co base composite cathode material is a negative electrode; In mould, successively place anode powder, electrolyte powder, cathode powder, battery cell is taked the form of anode-supported, in the moulding of 200MPa pressed.
The voltage and current of difference test battery two interpolars in 500 ℃～650 ℃ temperature ranges, the maximum power density of gained battery is 331mW/cm at 650 ℃
2
Claims (5)
1. Ca-Ti ore type Co base composite cathode material, by mass percentage, form by following component:
La
0.7Sr
0.15Ca
0.15Co
0.8Fe
0.2O
3-δ 50％
Ce
0.8Sm
0.2O
2-δ 37.5％
Li
2CO
3And Na
2CO
3The mixture of forming in 2: 1 in molar ratio 12.5%
2. the preparation method of Ca-Ti ore type Co base composite cathode material according to claim 1 is characterized in that: said La
0.7Sr
0.15Ca
0.15Co
0.8Fe
0.2O
3-δPreparation comprise the step of precursor preparation and calcining, said calcining step be with by the synthetic presoma of citrate method at 900 ℃～1000 ℃ microwave calcination 1.5～2h.
3. the preparation method of Ca-Ti ore type Co base composite cathode material according to claim 1 is characterized in that: said Ce
0.8Sm
0.2O
2-δPreparation comprise the step of precursor preparation and calcining, said calcining step be with by the synthetic presoma of citrate method at 900 ℃～1000 ℃ microwave calcination 1.5～2h, make the SDC powder.
4. according to the preparation method of the said Ca-Ti ore type Co base of claim 1 composite cathode material, it is characterized in that: the processing step of said Ca-Ti ore type Co base composite cathode material preparation is following:
A. taking by weighing mol ratio by 1/3rd of the said SDC powder quality of claim 3 is 2: 1 Li
2CO
3And Na
2CO
3Powder at 650 ℃ of following microwave calcination 0.5h, makes the CSC powder behind SDC powder and the carbonate mixed grinding;
B. with the said La of claim 2
0.7Sr
0.15Ca
0.15Co
0.8Fe
0.2O
3-δPowder and CSC powder mixed grinding after make Ca-Ti ore type Co base composite cathode material with mass ratio at 1: 1.
5. intermediate temperature solid oxide fuel cell, it is characterized in that: said fuel cell is prepared by following method:
A. by Li: Cu: the Ni mol ratio is to take by weighing Li at 1: 4: 5
2CO
3, CuO and NiO powder, at 650 ℃ of following microwave calcination 0.5h, make LCN anode powder behind the mixed grinding;
B. be anode material with LCN powder and CSC composite electrolyte powder with 1: 1 mixed grinding of mass ratio; With CSC powder or SDC powder as electrolyte; With the described Ca-Ti ore type Co base of claim 1 composite cathode material is negative electrode; In mould, successively place anode powder, electrolyte powder, cathode powder, monocell adopts the form of anode-supported, in the moulding of 200MPa pressed;
C. the effective active area 0.64cm of monocell
2, monocell is packed in the anchor clamps, adopt the silver slurry to be sealant;
D. battery is fuel with hydrogen, and air is an oxidant, and gas flow rate is 80～120mL/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210017638.7A CN102569786B (en) | 2012-01-19 | 2012-01-19 | Perovskite Co-based composite negative electrode material as well as preparation and application thereof |
Applications Claiming Priority (1)
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| CN104659378B (en) * | 2015-02-07 | 2016-11-23 | 大连理工大学 | A kind of intermediate temperature solid oxide fuel cell nanofiber composite cathode preparation method |
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| CN106602103A (en) * | 2016-12-23 | 2017-04-26 | 中国矿业大学(北京) | Quick self-heating starting method of solid oxide fuel cell and material |
| CN108682882A (en) * | 2018-06-15 | 2018-10-19 | 东莞中子科学中心 | A kind of oxygen ion conductor and its preparation method and application |
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