CN106876726A - A kind of preparation method of SOFC high-activity cathode steady in a long-term - Google Patents
A kind of preparation method of SOFC high-activity cathode steady in a long-term Download PDFInfo
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- CN106876726A CN106876726A CN201510919383.7A CN201510919383A CN106876726A CN 106876726 A CN106876726 A CN 106876726A CN 201510919383 A CN201510919383 A CN 201510919383A CN 106876726 A CN106876726 A CN 106876726A
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- Prior art keywords
- doping
- calcining
- casing play
- maceration extract
- solution
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- 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 present invention relates to a kind of preparation method of SOFC high-activity cathode steady in a long-term, methods described is realized by the way that compound maceration extract is impregnated into casing play by high-temperature calcination, is comprised the following steps：1) casing play is prepared；2) compound maceration extract is impregnated into casing play, calcining obtains negative electrode.
Description
Technical field
The invention belongs to field of solid oxide fuel, and in particular to a kind of soild oxide steady in a long-term
The preparation method of fuel cell high-activity cathode.
Background technology
SOFC (SOFC) is a kind of TRT that chemical energy is converted into electric energy.
Because operation temperature (1000 DEG C -600 DEG C) very high is to connector etc. in SOFC pile
The material of auxiliary facility proposes very high request, so as to drastically increase production cost.Reducing operation temperature can
To reduce material cost, but the cathode activity to battery proposes new requirement simultaneously.BSCF, LSCF, LSC,
The active cathode material high such as LSF easily reacts in preparation process with common electrolyte YSZ, by dipping
Method can avoid high-temperature burning process from alleviating the reaction with YSZ, but the nano material meeting that dipping method is obtained
It is particle coarsening in the process of running, cause the rapid decay of performance.
Therefore, this area is in the urgent need to a kind of SOFC high activity the moon that can be steady in a long-term
Pole.
The content of the invention
To overcome the cathode of solid oxide fuel cell nano particle in discharge process to be roughened, the invention provides
A kind of particle coarsening method of simple and effective suppression, by the maceration extract for mixing ion conductor and electronic conductor
The method for impregnating calcining has obtained the ion conductor and electronic conductor nano particle of mutual stabilization.
The preparation method bag of SOFC high-activity cathode steady in a long-term provided by the present invention
Include following steps：
(1) casing play is prepared；
(2) compound maceration extract is impregnated into casing play, high-temperature calcination obtains negative electrode.
The porosity of step (1) described casing play is in 20-60vol% in the present invention；Skeleton layer material meet not with
There is kickback in electrolyte and cathode material, specially zirconium oxide, yttria-stabilized zirconia, cerium oxide,
Gadolinium or samarium doping cerium oxide, aluminum oxide or magnesia.
Step (1) described casing play is after skeleton layer material is mixed with pore creating material, binding agent in the present invention
Coated by mud, silk-screen printing, a kind of method covering bath surface in rotary coating or solution samarium drop coating,
Obtained in 800-1300 DEG C of calcining；Pore creating material is graphite, starch or PMMA, PS, PVDF polymer, is glued
Knot agent is the mass ratio of PVB, ethyl cellulose or salicylic organic solution, pore creating material and skeleton layer material
The mass ratio 0.5-2 of 0.05-1, binding agent and skeleton layer material.
Dipping method in the present invention described in step (2) is solution impregnation-calcining-solution impregnation-calcining, is repeated
Solution impregnation-calcination process number of times 6-15 times.
Compound maceration extract in the present invention described in step (2) be the ammonium citrate of nitrate, glycine, urea,
One or two or more kinds complex liquid in EDTA；The metal species and ratio of nitrate are by electricity in the maceration extract
Sub- conductor/ion conductor molar ratio determines that electronic conductor/ion conductor molar ratio is 9/1-3/7.
Calcining heat in the present invention described in step (2) is 750 DEG C -1000 DEG C, calcination time 1-4h, from room
The heating rate that temperature is warmed up to calcining heat is 1-5 DEG C/min.
The ratio of metal ion is 1/1-2/1 in heretofore described complexing agent and nitrate.
Heretofore described electronic conductor is the lanthanum manganate of doping, the cobalt acid lanthanum of doping, the cadmium ferrite of doping or mixes
Miscellaneous barium ferrite perovskite material；Told ion conductor is zirconium oxide, the cerium oxide of doping or the doping adulterated
Bismuth oxide.
The beneficial effects of the invention are as follows：Solve asking for high-activity nano electrode stability prepared by dipping method
Topic；The preparation method of described SOFC high-activity cathode steady in a long-term is retaining dipping side
Method solves impregnated electrode due to nano-particle by ion conductor and the mutual stabilization of electronic conductor nano-particle
The rapid attenuation problem for being roughened and causing, while also improving the chemical property of negative electrode
Specific embodiment
Embodiment 1
By YSZ and 50wt% graphite and 100wt% negative electrodes glue (terpineol solution containing 6wt% ethyl celluloses)
It is coated on the two-in-one electrolyte YSZ surfaces of anode supported cells by way of mud is coated after mixing,
1200 DEG C of calcining 2h, skeleton layer porosity 70%.Nitrate is dissolved in the ratio of LSM/YSZ mol ratios 6/4
In water, it is complexed with 1.5 times of ammonium citrates, compound maceration extract is impregnated into casing play, is repeated 10 times, 850 DEG C
Calcining.Peak power is when 800 DEG C of the battery for obtaining uses hydrogen/oxygen for fuel gas and oxidizing gas
2.4Wcm-2, and attenuation rate in 100-1000h only has 0.02%.
Embodiment 2
By YSZ and 50wt%PMMA (average grain diameter 3um) and 150wt% negative electrodes glue, (ethyl containing 6wt% is fine
Tie up element terpineol solution) mixing after the two-in-one electricity of anode supported cells is coated to by way of silk-screen printing
On solution matter YSZ surfaces, 1100 DEG C of calcining 2h, skeleton layer porosity 80%.Nitrate presses LSC/GDC moles
Ratio than 7/3 is dissolved in the water, and is complexed with 1.2 times of ammonium citrates, and compound maceration extract is impregnated into casing play
In, it is repeated 8 times, 750 DEG C of calcinings.It is fuel gas and oxic gas that 700 DEG C of the battery for obtaining uses hydrogen/oxygen
Peak power is 1.8Wcm during body-2, and it is undamped in 500-1000h.
Embodiment 3
By Al2O3With 50wt%PMMA (average grain diameter 3um) and 100wt% negative electrodes glue (ethyl containing 6wt%
The terpineol solution of cellulose) that anode supported cells are coated to by way of silk-screen printing is two-in-one after mixing
On electrolyte YSZ surfaces, 1200 DEG C of calcining 2h, skeleton layer porosity 50%.Nitrate rubs by LSF/GDC
You are dissolved in the water at the ratio than 5/5, add 1.2 times of complexing of glycin with 1. times of EDTA, by compound dipping immersion
Stain is repeated 12 times in casing play, 800 DEG C of calcinings.It is combustion that 700 DEG C of the battery for obtaining uses hydrogen/oxygen
Peak power is 1.2Wcm during material gas and oxidizing gas-2, and it is substantially undamped in 400-1000h.
Claims (10)
1. a kind of preparation method of SOFC high-activity cathode steady in a long-term, it is characterised in that institute
The method of stating comprises the following steps：
(1) casing play is prepared；
(2) compound maceration extract is impregnated into casing play, high-temperature calcination obtains negative electrode.
2. method as claimed in claim 1, it is characterised in that the porosity of step (1) described casing play exists
20-60vol%.
3. method as claimed in claim 1, it is characterised in that step (1) the skeleton layer material meet not with electricity
Solution matter and cathode material occur kickback, specially zirconium oxide, yttria-stabilized zirconia, cerium oxide,
Gadolinium or samarium doping cerium oxide, aluminum oxide or magnesia.
4. such as the methods described of claim 1 or 3, it is characterised in that step (1) casing play is by by skeleton
Layer material is coated after mixing with pore creating material, binding agent by mud, silk-screen printing, rotary coating or solution
A kind of method covering bath surface in samarium drop coating, obtains in 800-1300 DEG C of calcining；Pore creating material is stone
Ink, starch or PMMA, PS, PVDF polymer, binding agent are PVB, ethyl cellulose or salicylic acid
Organic solution, the mass ratio 0.05-1 of pore creating material and skeleton layer material, binding agent and skeleton layer material
Mass ratio 0.5-2.
5. method as claimed in claim 1, it is characterised in that dipping method described in step (2) for solution impregnation-
Calcining-solution impregnation-calcining, repeats solution impregnation-calcination process number of times 6-15 times.
6. method as claimed in claim 1, it is characterised in that the compound maceration extract described in step (2) is nitrate
Ammonium citrate, glycine, urea, EDTA in one or two or more kinds complex liquid.
7. method as claimed in claim 6, the metal species of nitrate in its characterization step (2) described maceration extract
Determined by electronic conductor/ion conductor molar ratio with ratio, electronic conductor/ion conductor molar ratio is
9/1-3/7。
8. method as claimed in claim 1, it is characterised in that the calcining heat described in step (2) is 750 DEG C
- 1000 DEG C, calcination time 1-4h, the heating rate from room temperature to calcining heat is 1-5 DEG C/min.
9. method as claimed in claim 6, it is characterised in that the ratio of metal ion in the complexing agent and nitrate
It is 1/1-2/1.
10. method as claimed in claim 7, it is characterised in that the electronic conductor is the lanthanum manganate of doping, doping
The barium ferrite perovskite material of cobalt acid lanthanum, the cadmium ferrite of doping or doping；Told ion conductor is doping
Zirconium oxide, doping cerium oxide or doping bismuth oxide.
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| CN201510919383.7A CN106876726A (en) | 2015-12-12 | 2015-12-12 | A kind of preparation method of SOFC high-activity cathode steady in a long-term |
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Cited By (5)
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|---|---|---|---|---|
| CN108461759A (en) * | 2018-01-19 | 2018-08-28 | 合肥国轩高科动力能源有限公司 | A kind of method of the nano combined cathode material of infusion process preparation solid oxide fuel cell |
| CN108630949A (en) * | 2018-03-22 | 2018-10-09 | 潮州三环（集团）股份有限公司 | A kind of solid oxide fuel cell and preparation method thereof |
| CN108963216A (en) * | 2018-07-04 | 2018-12-07 | 湖南工学院 | A kind of nano-porous materials infiltration liquid and preparation method thereof |
| CN110407577A (en) * | 2019-07-26 | 2019-11-05 | 惠州市富济电子材料有限公司 | Ceramic membrane material, catalysis electrode and its preparation method and application |
| CN111244470A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Nano composite cathode and preparation and application thereof |
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| CN102683722A (en) * | 2012-05-25 | 2012-09-19 | 南京工业大学 | Solid oxide fuel cell composite cathode and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108461759A (en) * | 2018-01-19 | 2018-08-28 | 合肥国轩高科动力能源有限公司 | A kind of method of the nano combined cathode material of infusion process preparation solid oxide fuel cell |
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| CN111244470A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Nano composite cathode and preparation and application thereof |
| CN111244470B (en) * | 2018-11-29 | 2021-05-04 | 中国科学院大连化学物理研究所 | Nano composite cathode and preparation and application thereof |
| CN110407577A (en) * | 2019-07-26 | 2019-11-05 | 惠州市富济电子材料有限公司 | Ceramic membrane material, catalysis electrode and its preparation method and application |
| CN110407577B (en) * | 2019-07-26 | 2022-05-17 | 深圳市富济新材料科技有限公司 | Ceramic film material, catalytic electrode, preparation method and application thereof |
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Application publication date: 20170620 |