CN102569786B - 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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- CN102569786B CN102569786B CN201210017638.7A CN201210017638A CN102569786B CN 102569786 B CN102569786 B CN 102569786B CN 201210017638 A CN201210017638 A CN 201210017638A CN 102569786 B CN102569786 B CN 102569786B
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- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000446 fuel Substances 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims description 63
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 57
- 239000003792 electrolyte Substances 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 13
- 229910002651 NO3 Inorganic materials 0.000 claims description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 229910002437 Ce0.8Sm0.2O2−δ Inorganic materials 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 5
- 238000005485 electric heating Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 206010013786 Dry skin Diseases 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 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
- 238000003756 stirring Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims 1
- 239000002243 precursor Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 abstract description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 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
- 239000010406 cathode material Substances 0.000 description 11
- 239000011533 mixed conductor Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910052772 Samarium Inorganic materials 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
- 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
- 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
- 239000004020 conductor Substances 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
- 238000005303 weighing Methods 0.000 description 2
- 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
- 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
- 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
Classifications
-
- 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
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 Synthesis and applications thereof, relate to intermediate temperature solid oxide fuel cell field, belong to new energy materials field.
Background technology
Solid Oxide Fuel Cell (SOFC, solid oxide fuel cell) be a kind of energy conversion device directly chemical energy of fuel gas and oxidizing gas being converted to the total solids assembly of electric energy, there is clean and efficient advantage, be thus referred to as the green energy resource of 21st century.
At present, traditional cathode material lanthanum manganate is under the condition of middle temperature, namely less than 800 DEG C, conductivity reduces rapidly, polarization resistance increases rapidly, be difficult to the requirement meeting intermediate temperature solid oxide fuel cell (ITSOFC, Intermediatetemperature solid oxide fuel cell).One of path addressed these problems is exactly find suitable electrode material, requires that these electrode materials and electrolyte match and electro-chemical activity is high, thus reduces the polarization resistance of battery, is applicable to battery at middle low operating temperatures.
The research of ITSOFC novel cathode material mainly concentrates on ABO
3on type perovskite structure electronics-cation mixed conductor, wherein, La
1-xsr
xco
1-yfe
yo
3(LSCF) system the most people paid attention to.At 800 DEG C, the electronic conductivity of LSCF system reaches 10
2~ 10
3s/cm, oxonium ion is conducted by Lacking oxygen flooding mechanism, can reach 10
-2the oxygen ionic conductivity of ~ 100S/cm, but the thermal coefficient of expansion of LSCF system is high, with CeO
2base electrolyte thermal matching is not inconsistent, and the Ca that singly adulterates
2+la
1-xca
xco
1-yfe
yo
3cathode material thermal coefficient of expansion is lower, and electrical property is poor.
Summary of the invention
The object of this invention is to provide a kind of perovskite Co-based composite negative electrode 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 of the samarium doping with fluorite structure, and proton conductor is carbonate, and wherein the cerium base oxide of samarium doping and the mixture of carbonate form oxonium ion-proton mixed conductor.
The technical scheme that the present invention deals with problems is a kind of perovskite Co-based composite negative electrode material, by mass percentage, is made up of following component:
La
0.7Sr
0.15Ca
0.15Co
0.8Fe
0.2O
3-δ50％
Ce
0.8Sm
0.2O
2-δ37.5％
Li
2cO
3and Na
2cO
3the mixture 12.5% of 2: 1 compositions in molar ratio
Another object of the present invention is to provide the preparation method of above-mentioned perovskite Co-based composite negative electrode 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 perovskite Co-based composite negative electrode material.
1. electronics-oxonium ion mixed conductor La
0.7sr
0.15ca
0.15co
0.8fe
0.2o
3-δprepared by cathode material:
A. by 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-δstoichiometric proportion weigh after, with distilled water dissolve, formed nitrate mixed solution; Be take citric acid at 1.5 ~ 2: 1 according to metal ion mol ratio in citric acid and nitrate mixed solution, dissolve citric acid with distilled water;
B. citric acid solution is poured in nitrate mixed solution, regulate pH to be 2 with ammoniacal liquor;
C. step b is obtained mixed solution to stir at 65 ~ 75 DEG C of lower magnetic forces, until form gel; Gel is placed in electric heating constant-temperature blowing drying box and obtains presoma in 120 DEG C of dryings;
D. by synthesis presoma at 900 DEG C ~ 1000 DEG C microwave calcination 1.5 ~ 2h.
2. oxygen ion conductor Ce
0.8sm
0.2o
2-δpreparation:
A. Ce is pressed
0.8sm
0.2o
2-δstoichiometric proportion raw materials weighing, with red fuming nitric acid (RFNA) dissolved oxygen samarium, dissolve cerous nitrate and citric acid with distilled water;
B. samarium nitrate solution is poured in cerous nitrate solution, then citric acid is poured in nitrate mixed solution, by ammoniacal liquor adjust ph to 8;
C. mixed solution is stirred at 65 ~ 75 DEG C of lower magnetic forces, until form gel; Gel is placed in electric heating constant-temperature blowing drying box, and at 120 DEG C, dry 2h obtains presoma;
D. by synthesis presoma at 900 DEG C ~ 1000 DEG C microwave calcination 1.5 ~ 2h, obtain samarium doping cerium oxide (SDC, samarium doped ceria) electrolyte powder.
3. perovskite Co-based composite negative electrode material preparation:
A. Li is taken by 1/3rd of SDC electrolyte powder weight
2cO
3and Na
2cO
3powder, wherein Li
2cO
3with Na
2cO
3mol ratio be after 2: 1, SDC powder and carbonate mixed grinding at 650 DEG C microwave calcination 0.5h, obtained SDC and carbonate composite electrolyte powder (CSC, ceria-salt-composite);
B. by La
0.7sr
0.15ca
0.15co
0.8fe
0.2o
3-δpowder and CSC composite electrolyte powder are with perovskite Co-based composite negative electrode material obtained after mass ratio 1: 1 mixed grinding.
Another object of the present invention is to provide a kind of intermediate temperature solid oxide fuel cell, and this fuel cell is with Ca-Ti ore type Co based composites for cathode material, and preparation method is as follows:
A. be take Li at 1: 4: 5 by Li: Cu: Ni mol ratio
2cO
3, CuO and NiO powder, after mixed grinding at 650 DEG C microwave calcination 0.5h, obtained Li
2cO
3-CuO-NiO (LCN) anode powder;
B. by LCN powder and CSC composite electrolyte powder with mass ratio 1: 1 mixed grinding for anode material, using CSC powder or SDC powder as electrolyte, perovskite Co-based composite negative electrode material is negative electrode, successively place anode powder, electrolyte powder, cathode powder in a mold, the form of anode-supported taked by monocell, compressing under 200MPa.
C. monocell effective activation area 0.64cm
2, monocell is loaded in fixture, adopts silver slurry to be sealant.
D. battery take hydrogen as fuel, and air is oxidant, and gas flow rate is 80 ~ 120mL/min.
The invention has the beneficial effects as follows: codope perovskite Co-based composite negative electrode material in A position disclosed by the invention not only has high electronics, ionic conductivity, also there is higher middle temperature catalytic activity and excellent chemical property.In hot property and chemical property, there is good compatibility with cerium base electrolyte material, as the negative electrode of middle temperature solid oxidized fuel cell, there is higher power output.
Accompanying drawing explanation
Accompanying drawing of the present invention is 2 width,
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 the present invention of those of ordinary skill in the art's comprehend, 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-δprepared by cathode material
A. by 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) is by La
0.7sr
0.15ca
0.15co
0.8fe
0.2o
3-δstoichiometric proportion weigh after, with distilled water dissolve, formed nitrate mixed solution; Be take citric acid at 1.5: 1 according to the mol ratio of citric acid (AR) and metal ion, dissolve citric acid with distilled water;
B. citric acid solution is poured in nitrate mixed solution, regulate pH to be 2 with ammoniacal liquor;
C. stirred at 65 ~ 75 DEG C of lower magnetic forces by mixed solution, along with the continuous evaporation of solvent, solution gradually retrogradation finally forms gel; Gel is placed in electric heating constant-temperature blowing drying box and obtains presoma in 120 DEG C of dryings;
D. by presoma microwave calcination 2h at 900 DEG C, the electronics-oxonium ion mixed conductor La of obtained 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. Ce is pressed
0.8sm
0.2o
2-δstoichiometric proportion raw materials weighing, use dense HNO
3(>=99.5%) dissolved oxygen samarium (>=99.0%), dissolves cerous nitrate (>=99.0%) and citric acid (AR) with distilled water;
B. samarium nitrate solution is poured in cerous nitrate solution, then citric acid is poured in nitrate mixed solution, by ammoniacal liquor adjust ph to 8;
C. mixed solution is stirred at 65 ~ 75 DEG C of lower magnetic forces, until form gel; Gel is placed in electric heating constant-temperature blowing drying box, and at 120 DEG C, dry 2h obtains presoma;
D. by presoma microwave calcination 1.5h at 900 DEG C, obtained SDC electrolyte powder.
Fig. 2 is the XRD spectra of SDC powder and CSC powder, is wherein fluorite type structure according to the collection of illustrative plates of SDC powder.
3. perovskite Co-based composite negative electrode material preparation
A. first Li is taken with 1/3rd of SDC electrolyte powder weight
2cO
3(is produced from Hunan,>=96.0%) and Na
2cO
3(is produced from Beijing,>=99.8%) powder, wherein Li
2cO
3with Na
2cO
3mol ratio be 2: 1.After SDC powder and carbonate mixed grinding at 650 DEG C microwave calcination 0.5h, obtained CSC (CSC, ceria-salt-composite) compound electrolyte material;
B. by La
0.7sr
0.15ca
0.15co
0.8fe
0.2o
3-δwith CSC composite electrolyte powder with perovskite Co-based composite negative electrode material obtained after mass ratio 1: 1 mixed grinding.
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 it and is fluorite type structure, after SDC powder and carbonate mixed calcining are described, does not generate new component.
4. Solid Oxide Fuel Cell preparation
A. Li is taken with Li: Cu: Ni mol ratio 1: 4: 5
2cO
3, CuO (>=99.0%) and NiO (>=99.0%) powder, after mixed grinding at 650 DEG C microwave calcination 0.5h, obtained LCN anode powder.
B.LCN powder and CSC composite electrolyte powder are with mass ratio 1: 1 mixed grinding for anode, and with CSC powder for dielectric substrate, prepared perovskite Co-based composite negative electrode material is negative electrode; Successively place anode powder, electrolyte powder, cathode powder in a mold, the form of anode-supported taked by monocell, compressing under 200MPa.
C. monocell effective activation area 0.64cm
2, monocell is loaded in fixture, adopts silver slurry to be sealant.
D. battery take hydrogen as fuel, and air is oxidant, and gas flow rate is 80 ~ 120mL/min.
The voltage and current of difference test battery two interpolar in 500 DEG C ~ 650 DEG C temperature ranges, the maximum power density of gained battery is 584.1mW/cm at 650 DEG C
2.
Embodiment 2
1. electronics-oxonium ion mixed conductor La
0.7sr
0.15ca
0.15co
0.8fe
0.2o
3-δcathode material synthesizes
A. by 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 stoichiometric proportion weighs, dissolve with distilled water, form nitrate mixed solution; Be take citric acid at 2: 1 according to the mol ratio of metal ion in citric acid and nitrate mixed solution, dissolve citric acid with distilled water.
B. with embodiment 1.
C. with embodiment 1.
D. by presoma microwave calcination 1.5h at 1000 DEG C, the electronics-oxonium ion mixed conductor La of obtained 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. b step is as follows, and other steps are with embodiment 1:
B.LCN powder and CSC composite electrolyte powder are with mass ratio 1: 1 mixed grinding for anode, and with SDC powder for dielectric substrate, prepared perovskite Co-based composite negative electrode material is negative electrode; Successively place anode powder, electrolyte powder, cathode powder in a mold, battery cell takes the form of anode-supported, compressing under 200MPa.
The voltage and current of difference test battery two interpolar in 500 DEG C ~ 650 DEG C temperature ranges, the maximum power density of gained battery is 331mW/cm at 650 DEG C
2.
Claims (1)
1. an intermediate temperature solid oxide fuel cell, is characterized in that: described fuel cell is prepared by following method:
A. be that 1:4:5 takes Li by Li:Cu:Ni mol ratio
2cO
3, CuO and NiO powder, after mixed grinding at 650 DEG C microwave calcination 0.5h, obtained LCN anode powder;
B. by LCN powder and CSC composite electrolyte powder with mass ratio 1:1 mixed grinding for anode material, using CSC powder or SDC powder as electrolyte, take perovskite Co-based composite negative electrode material as negative electrode, successively place anode powder, electrolyte powder, cathode powder in a mold, monocell adopts the form of anode-supported, compressing under 200MPa;
C. monocell effective activation area 0.64cm
2, monocell is loaded in fixture, adopts silver slurry to be sealant;
D. battery take hydrogen as fuel, and air is oxidant, and gas flow rate is 80 ~ 120mL/min;
Wherein, described perovskite Co-based composite negative electrode material, by mass percentage, is made up of following component:
La
0.7Sr
0.15Ca
0.15Co
0.8Fe
0.2O
3-δ50％
Ce
0.8Sm
0.2O
2-δ37.5％
Li
2cO
3and Na
2cO
3the mixture 12.5% of 2:1 composition in molar ratio,
Wherein, described La
0.7sr
0.15ca
0.15co
0.8fe
0.2o
3-δprepare as follows:
A. by 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-δstoichiometric proportion weigh after, with distilled water dissolve, formed nitrate mixed solution; Be that 1.5 ~ 2:1 takes citric acid according to metal ion mol ratio in citric acid and nitrate mixed solution, dissolve citric acid with distilled water;
B. citric acid solution is poured in nitrate mixed solution, regulate pH to be 2 with ammoniacal liquor;
C. step b is obtained mixed solution to stir at 65 ~ 75 DEG C of lower magnetic forces, until form gel; Gel is placed in electric heating constant-temperature blowing drying box and obtains presoma in 120 DEG C of dryings;
D. by synthesis presoma at 900 DEG C ~ 1000 DEG C microwave calcination 1.5 ~ 2h;
Described Ce
0.8sm
0.2o
2-δpreparation comprise the step of precursor power and calcining, described calcining step is by the presoma that synthesized by citrate method at 900 DEG C ~ 1000 DEG C microwave calcination 1.5 ~ 2h, obtained SDC powder;
The Li that mol ratio is 2:1 is taken by 1/3rd of SDC powder quality
2cO
3and Na
2cO
3powder, after SDC powder and carbonate mixed grinding at 650 DEG C microwave calcination 0.5h, obtained CSC powder; By La
0.7sr
0.15ca
0.15co
0.8fe
0.2o
3-δpowder and CSC powder are with perovskite Co-based composite negative electrode material obtained after mass ratio 1:1 mixed grinding.
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 |
| CN106467315B (en) * | 2015-08-17 | 2017-12-15 | 天津包钢稀土研究院有限责任公司 | One pot of precipitation method prepares Ce0.8Sm0.2O1.9‑La1‑xSrxFe1‑yCoyO3‑δThe method of superfine powder |
| 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 |
| CN108808047A (en) * | 2018-05-07 | 2018-11-13 | 湖北大学 | LSCF/Na2CO3Nanocomposite is the preparation method of fuel cell ion transport layer |
| CN108682882B (en) * | 2018-06-15 | 2021-08-03 | 散裂中子源科学中心 | Oxygen ion conductor and preparation method and application thereof |
| CN108832136B (en) * | 2018-06-21 | 2020-10-23 | 中国科学院上海应用物理研究所 | Composite oxygen electrode for solid oxide battery and preparation method thereof |
| CN111554956B (en) * | 2020-04-02 | 2021-11-23 | 湖北大学 | LST-SDC-NCAL composite material and application thereof, single-layer fuel cell and preparation method thereof |
| CN111389406B (en) * | 2020-04-29 | 2023-02-03 | 华东师范大学 | Preparation method and electrocatalysis application of perovskite electrode material |
| CN112687900B (en) * | 2020-12-29 | 2022-07-26 | 深圳大学 | Electric energy-value-added chemical symbiotic fuel cell and preparation method thereof |
| CN113258086B (en) * | 2021-04-30 | 2022-09-27 | 南京工业大学 | Three-phase conductor proton conductor composite cathode material and preparation method thereof |
| CN113745548B (en) * | 2021-09-09 | 2023-03-31 | 南华大学 | High-entropy ceramic material based on spinel structure and preparation method and application thereof |
| CN114420943A (en) * | 2022-01-13 | 2022-04-29 | 上海交通大学 | Heterogeneous interface composite electrode material and preparation method and application thereof |
| CN114956208A (en) * | 2022-06-22 | 2022-08-30 | 合肥国轩高科动力能源有限公司 | High-nickel ternary cathode material, preparation method thereof and application thereof in battery preparation |
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