CN101308930A - Preparing method of methane direct oxidized anode - Google Patents
Preparing method of methane direct oxidized anode Download PDFInfo
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- CN101308930A CN101308930A CNA2008100646314A CN200810064631A CN101308930A CN 101308930 A CN101308930 A CN 101308930A CN A2008100646314 A CNA2008100646314 A CN A2008100646314A CN 200810064631 A CN200810064631 A CN 200810064631A CN 101308930 A CN101308930 A CN 101308930A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
Disclosed is a method to prepare anode which is directly oxidated with methane, relating to a solid fuel cell anode fabrication method, solving the problems of complex process, high sintering temperature, low catalytic activity of NiO and CeO2 in current methods to fabricate anodes which are directly oxidated with methane. The method includes the following steps: firstly, preparing porous YSZ tape-casting slurry; secondly, preparing compact YSZ tape-casting slurry; thirdly, preparing compact YSZ biscuit film; fourthly, preparing a porous YSZ composite compact YSZ biscuit; fifthly, sintering the porous YSZ composite compact YSZ biscuit to get a porous YSZ composite compact YSZ matrix; sixthly, immersing the porous YSZ composite compact YSZ matrix in the mixture of nickel nitrate and cerium nitrate; after drying and calcining, anode directly oxidated with methane can be obtained. The anode is good in property and simple in technique, and the NiO and CeO2 are of low calcining temperature and high catalytic activity.
Description
Technical field
The present invention relates to a kind of preparation method of anode.
Background technology
Solid Oxide Fuel Cell (SOFC) is as a kind of electrochemical power generator, have advantages such as efficient, environmental protection, suitability of fuel be strong, soild oxide can make the comprehensive utilization ratio of natural gas resource reach 60～80% in theory, so methane direct oxidized anode is one of research emphasis of SOFC.CeO
2Or the CeO that mixes
2Have higher oxygen storage and transmittability and become the research focus of SOFC direct oxidation anode, therefore, the Ni/YSZ anode that is applied in the various anode materials of SOFC is the dominant direction of this area research all the time, and by adding CeO
2Or the CeO that mixes
2Improve the anti-carbon deposit and the catalytic activity of Ni-YSZ anode material.
Utilize CeO at present
2The method of Ni-YSZ anode performance comprised when improvement was fuel with methane: dual-layered anode structure and solid phase synthesis, still, the complex manufacturing technology of dual-layered anode structure structure wherein; In the solid phase synthesis, obtain NiO-CeO
2/ YSZ anode is adding NiO-CeO
2After also will be through temperature sintering up to 1400～1500 ℃, and NiO is behind high temperature sintering, its catalytic activity reduces, CeO
2When tying with the YSZ high temperature co-firing, CeO
2Form Zr-Ce solid solution with the Zr among the YSZ, can reduce CeO
2Catalytic activity, thereby reduced electrode performance.
Summary of the invention
The present invention seeks to complex process, sintering temperature height, NiO and CeO in order to solve the prior art for preparing methane direct oxidized anode
2The problem of the low and electrode performance difference of catalytic activity, and provide a kind of preparation method of methane direct oxidized anode.
The preparation method of methane direct oxidized anode realizes according to the following steps: one, press mass ratio 60～65: 100 with starch and the mixing of YSZ powder, add organic solvent and dispersant ball milling 22～26h then, add binding agent and plastic agent mixing and ball milling 22～26h again, obtain the casting slurry of porous YSZ; Two, with YSZ powder, organic solvent and dispersant ball milling 22～26h, add binding agent and plastic agent mixing and ball milling 22～26h then, obtain compact YSZ tape-casting slurry; Three, compact YSZ tape-casting slurry is carried out vacuumizing and defoaming, then in casting machine film band upper reaches one deck compact YSZ tape-casting slurry, drying forms compact YSZ biscuit film; Four, the casting slurry with porous YSZ carries out vacuumizing and defoaming, and at the casting slurry of compact YSZ biscuit film upper reaches one deck porous YSZ, drying forms porous YSZ composite compact YSZ biscuit then; Five, porous YSZ composite compact YSZ biscuit is put into sintering 4～6h under 1400～1500 ℃ the condition, the porous YSZ composite compact YSZ matrix; Six, press Ni and CeO
29～5: 1～2 the mass ratio preparation nickel nitrate and the mixed solution of cerous nitrate, under vacuum condition, the porous YSZ composite compact YSZ matrix is immersed in the mixed solution and takes out behind 2～3h, dry 10～14h under 70～90 ℃ condition then, put into roasting 0.4～0.6h under 700～900 ℃ the condition again, promptly get methane direct oxidized anode; Identical organic solvent, identical dispersant, identical binding agent and identical plastic agent have wherein been used in the step 1 and two, and the mass ratio of YSZ powder and organic solvent is 1: 1.1～1.7 among step 1 and two, the mass ratio of YSZ powder and dispersant is 1: 0.025～0.035, the mass ratio of YSZ powder and binding agent is 1: 0.08～0.12, and the mass ratio of YSZ powder and plastic agent is 1: 0.15～0.21.
Used hybrid infusion method among the present invention, make in the product Ni content lower, because the battery structure that the Ni sintering and the contraction of expanding thereof cause destroys and battery performance descends, (maximum power density of battery is 350～360mW/cm so electrode performance is good in the time of can slowing down battery operation
2), and under the condition of vacuumizing, be impregnated with and be beneficial to the distribution of active material in the porous YSZ composite compact YSZ matrix, and the sintering temperature of matrix after flooding in the mixed solution of nickel nitrate and cerous nitrate is lower, makes NiO and CeO
2The catalytic activity height.Technology of the present invention is simple, easily control.
Embodiment
Embodiment one: the preparation method of present embodiment methane direct oxidized anode realizes according to the following steps: one, press mass ratio 60～65: 100 with starch and the mixing of YSZ powder, add organic solvent and dispersant ball milling 22～26h then, add binding agent and plastic agent mixing and ball milling 22～26h again, obtain the casting slurry of porous YSZ; Two, with YSZ powder, organic solvent and dispersant ball milling 22～26h, add binding agent and plastic agent mixing and ball milling 22～26h then, obtain compact YSZ tape-casting slurry; Three, compact YSZ tape-casting slurry is carried out vacuumizing and defoaming, then in casting machine film band upper reaches one deck compact YSZ tape-casting slurry, drying forms compact YSZ biscuit film; Four, the casting slurry with porous YSZ carries out vacuumizing and defoaming, and at the casting slurry of compact YSZ biscuit film upper reaches one deck porous YSZ, drying forms porous YSZ composite compact YSZ biscuit then; Five, porous YSZ composite compact YSZ biscuit is put into sintering 4～6h under 1400～1500 ℃ the condition, the porous YSZ composite compact YSZ matrix; Six, press Ni and CeO
29～5: 1～2 the mass ratio preparation nickel nitrate and the mixed solution of cerous nitrate, under vacuum condition, the porous YSZ composite compact YSZ matrix is immersed in the mixed solution and takes out behind 2～3h, dry 10～14h under 70～90 ℃ condition then, put into roasting 0.4～0.6h under 700～900 ℃ the condition again, promptly get methane direct oxidized anode; Identical organic solvent, identical dispersant, identical binding agent and identical plastic agent have wherein been used in the step 1 and two, and the mass ratio of YSZ powder and organic solvent is 1: 1.1～1.7 among step 1 and two, the mass ratio of YSZ powder and dispersant is 1: 0.025～0.035, the mass ratio of YSZ powder and binding agent is 1: 0.08～0.12, and the mass ratio of YSZ powder and plastic agent is 1: 0.15～0.21.
Embodiment two: present embodiment and embodiment one are different is by mass ratio 62: 100 starch and YSZ powder to be mixed in the step 1, add organic solvent and dispersant ball milling 24h then, add binding agent and plastic agent mixing and ball milling 24h again.Other step and parameter are identical with embodiment one.
Carrying out mixing and ball milling in the present embodiment is that the employing diameter is the zirconium oxide balls of 5～15mm, mixes with the speed of 100～200r/min.
Embodiment three: present embodiment and embodiment one are different is that organic solvent is two kinds a azeotropic mixture in ethanol, methylethylketone, the trichloroethylene in the step 1.Other step and parameter are identical with embodiment one.
Embodiment four: what present embodiment and embodiment one were different is that dispersant is the phosphoric acid ester dispersant in the step 1.Other step and parameter are identical with embodiment one.
Embodiment five: what present embodiment and embodiment one were different is that binding agent is polyvinyl butyral resin, polymethyl acrylate or ethyl cellulose in the step 1.Other step and parameter are identical with embodiment one.
Embodiment six: what present embodiment and embodiment one were different is that plastic agent is polyethylene glycol and diethyl phthalate in the step 1.Other step and parameter are identical with embodiment one.
The mass ratio of polyethylene glycol and diethyl phthalate is 0.08～0.11: 0.07～0.10 in the present embodiment.
Embodiment seven: present embodiment and embodiment one are different be in the step 2 with YSZ powder, organic solvent and dispersant ball milling 24h, add binding agent and plastic agent mixing and ball milling 24h then.Other step and parameter are identical with embodiment one.
Embodiment eight: what present embodiment and embodiment one were different is the repetitive operation step 4.Other step and parameter are identical with embodiment one.
The number of times of present embodiment repetitive operation step 4 is determined by the porous YSZ composite compact YSZ biscuit design thickness.
Embodiment nine: present embodiment and embodiment one are different is in the step 5 porous YSZ composite compact YSZ biscuit to be put into sintering 5h under 1450 ℃ the condition.Other step and parameter are identical with embodiment one.
Embodiment ten: what present embodiment and embodiment one were different is by Ni and CeO in the step 6
2The mixed solution of 5: 2 mass ratio preparation nickel nitrate and cerous nitrate is immersed in the porous YSZ composite compact YSZ matrix in the mixed solution under vacuum condition and takes out behind the 2.5h, and dry 12h under 80 ℃ condition then puts into roasting 0.5h under 800 ℃ the condition again.Other step and parameter are identical with embodiment one.
Repetitive operation dipping, drying and roasting can reach the carrying capacity of needed Solid Oxide Fuel Cell methane direct oxidized anode in the present embodiment.
Embodiment 11: the preparation method of present embodiment methane direct oxidized anode realizes according to the following steps: one, press mass ratio 65: 100 starch and YSZ powder are mixed, add organic solvent and dispersant ball milling 24h then, add binding agent and plastic agent mixing and ball milling 24h again, obtain the casting slurry of porous YSZ; Two, with YSZ powder, organic solvent and dispersant ball milling 24h, add binding agent and plastic agent mixing and ball milling 24h then, obtain compact YSZ tape-casting slurry; Three, compact YSZ tape-casting slurry is carried out vacuumizing and defoaming, then in casting machine film band upper reaches one deck compact YSZ tape-casting slurry, drying forms compact YSZ biscuit film; Four, the casting slurry with porous YSZ carries out vacuumizing and defoaming, and at the casting slurry of compact YSZ biscuit film upper reaches one deck porous YSZ, drying forms porous YSZ composite compact YSZ biscuit then; Five, porous YSZ composite compact YSZ biscuit is put into sintering 6h under 1500 ℃ the condition, the porous YSZ composite compact YSZ matrix; Six, press Ni and CeO
25: 2 the mass ratio preparation nickel nitrate and the mixed solution of cerous nitrate, under vacuum condition, the porous YSZ composite compact YSZ matrix is immersed in the mixed solution and takes out behind the 2.5h, dry 12h under 80 ℃ condition then, put into roasting 0.5h under 800 ℃ the condition again, promptly get methane direct oxidized anode; Identical organic solvent, identical dispersant, identical binding agent and identical plastic agent have wherein been used in the step 1 and two, and the mass ratio of YSZ powder and organic solvent is 1: 1.4 among step 1 and two, the mass ratio of YSZ powder and dispersant is 1: 0.03, the mass ratio of YSZ powder and binding agent is 1: 0.1, and the mass ratio of YSZ powder and plastic agent is 1: 0.18.
Repetitive operation dipping in the present embodiment, drying and roasting 9 times can reach the carrying capacity of needed Solid Oxide Fuel Cell methane direct oxidized anode, and it is assembled into Solid Oxide Fuel Cell, and the maximum power density of its battery is 360mW/cm
2, this shows that electrode performance is better.
Claims (10)
1, a kind of preparation method of methane direct oxidized anode, the preparation method who it is characterized in that methane direct oxidized anode realizes according to the following steps: one, press mass ratio 60～65: 100 with starch and the mixing of YSZ powder, add organic solvent and dispersant ball milling 22～26h then, add binding agent and plastic agent mixing and ball milling 22～26h again, obtain the casting slurry of porous YSZ; Two, with YSZ powder, organic solvent and dispersant ball milling 22～26h, add binding agent and plastic agent mixing and ball milling 22～26h then, obtain compact YSZ tape-casting slurry; Three, compact YSZ tape-casting slurry is carried out vacuumizing and defoaming, then in casting machine film band upper reaches one deck compact YSZ tape-casting slurry, drying forms compact YSZ biscuit film; Four, the casting slurry with porous YSZ carries out vacuumizing and defoaming, and at the casting slurry of compact YSZ biscuit film upper reaches one deck porous YSZ, drying forms porous YSZ composite compact YSZ biscuit then; Five, porous YSZ composite compact YSZ biscuit is put into sintering 4～6h under 1400～1500 ℃ the condition, the porous YSZ composite compact YSZ matrix; Six, press Ni and CeO
29～5: 1～2 the mass ratio preparation nickel nitrate and the mixed solution of cerous nitrate, under vacuum condition, the porous YSZ composite compact YSZ matrix is immersed in the mixed solution and takes out behind 2～3h, dry 10～14h under 70～90 ℃ condition then, put into roasting 0.4～0.6h under 700～900 ℃ the condition again, promptly get methane direct oxidized anode; Identical organic solvent, identical dispersant, identical binding agent and identical plastic agent have wherein been used in the step 1 and two, and the mass ratio of YSZ powder and organic solvent is 1: 1.1～1.7 among step 1 and two, the mass ratio of YSZ powder and dispersant is 1: 0.025～0.035, the mass ratio of YSZ powder and binding agent is 1: 0.08～0.12, and the mass ratio of YSZ powder and plastic agent is 1: 0.15～0.21.
2, the preparation method of methane direct oxidized anode according to claim 1, it is characterized in that in the step 1 starch and YSZ powder being mixed by mass ratio 62: 100, add organic solvent and dispersant ball milling 24h then, add binding agent and plastic agent mixing and ball milling 24h again.
3, the preparation method of methane direct oxidized anode according to claim 1 is characterized in that organic solvent in the step 1 is two kinds a azeotropic mixture in ethanol, methylethylketone, the trichloroethylene.
4, the preparation method of methane direct oxidized anode according to claim 1 is characterized in that dispersant is the phosphoric acid ester dispersant in the step 1.
5, the preparation method of methane direct oxidized anode according to claim 1 is characterized in that binding agent is polyvinyl butyral resin, polymethyl acrylate or ethyl cellulose in the step 1.
6, the preparation method of methane direct oxidized anode according to claim 1 is characterized in that plastic agent is polyethylene glycol and diethyl phthalate in the step 1.
7, the preparation method of methane direct oxidized anode according to claim 1 is characterized in that in the step 2 YSZ powder, organic solvent and dispersant ball milling 24h are added binding agent and plastic agent mixing and ball milling 24h then.
8, the preparation method of methane direct oxidized anode according to claim 1 is characterized in that the repetitive operation step 4.
9, the preparation method of methane direct oxidized anode according to claim 1 is characterized in that in the step 5 porous YSZ composite compact YSZ biscuit put into sintering 5h under 1450 ℃ the condition.
10, the preparation method of methane direct oxidized anode according to claim 1 is characterized in that in the step 6 by Ni and CeO
2The mixed solution of 5: 2 mass ratio preparation nickel nitrate and cerous nitrate is immersed in the porous YSZ composite compact YSZ matrix in the mixed solution under vacuum condition and takes out behind the 2.5h, and dry 12h under 80 ℃ condition then puts into roasting 0.5h under 800 ℃ the condition again.
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| CNA2008100646314A CN101308930A (en) | 2008-05-30 | 2008-05-30 | Preparing method of methane direct oxidized anode |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102185148A (en) * | 2011-04-01 | 2011-09-14 | 景德镇陶瓷学院 | NiO-based SOFC (Solid Oxide Fuel Cell) composite anode film material with nano-sheet microcellular structure and preparation method thereof |
| CN102332588A (en) * | 2011-10-17 | 2012-01-25 | 哈尔滨工业大学 | Method for preparing anode of solid oxide fuel cell by using immersion method |
| CN102364737A (en) * | 2011-10-12 | 2012-02-29 | 景德镇陶瓷学院 | Method for preparing anti-carbon composite cathode film material of flat plate type solid oxide fuel cell (SOFC) |
| CN104662712B (en) * | 2012-09-27 | 2017-04-12 | 丰田自动车株式会社 | Electrode paste production method and secondary battery |
-
2008
- 2008-05-30 CN CNA2008100646314A patent/CN101308930A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102185148A (en) * | 2011-04-01 | 2011-09-14 | 景德镇陶瓷学院 | NiO-based SOFC (Solid Oxide Fuel Cell) composite anode film material with nano-sheet microcellular structure and preparation method thereof |
| CN102364737A (en) * | 2011-10-12 | 2012-02-29 | 景德镇陶瓷学院 | Method for preparing anti-carbon composite cathode film material of flat plate type solid oxide fuel cell (SOFC) |
| CN102332588A (en) * | 2011-10-17 | 2012-01-25 | 哈尔滨工业大学 | Method for preparing anode of solid oxide fuel cell by using immersion method |
| CN102332588B (en) * | 2011-10-17 | 2014-01-29 | 哈尔滨工业大学 | Method for preparing anode of solid oxide fuel cell by using immersion method |
| CN104662712B (en) * | 2012-09-27 | 2017-04-12 | 丰田自动车株式会社 | Electrode paste production method and secondary battery |
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Open date: 20081119 |