CN1464577A - Moderate temperature solid oxide fuel battery composite double layer anode and process for preparing - Google Patents
Moderate temperature solid oxide fuel battery composite double layer anode and process for preparing Download PDFInfo
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- CN1464577A CN1464577A CN02124836A CN02124836A CN1464577A CN 1464577 A CN1464577 A CN 1464577A CN 02124836 A CN02124836 A CN 02124836A CN 02124836 A CN02124836 A CN 02124836A CN 1464577 A CN1464577 A CN 1464577A
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- nio
- composite double
- double layer
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- polyvinyl butyral
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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
A moderate temperature solid oxide fuel battery composite double layer anode, comprising of current collecting layer NiO-YSZ and active electrochemical reaction layer nickelous nitrate decomposition NiO-YSZ. First mix NiO by 30%-75% with YSZ, roll it along with polyvinyl butyral butyladehyde agglomerant to form anode current collecting layer, then mix nickel nitrate with 800 degree decomposition NiO and YSZ, roll it along with agglomerant to form active electrochemical reaction layer, combine the two layers and roll it into a composite double layer anode. Finally prepare YSZ film solid electrolyte on the composite double layer anode, heat-up at 230-1400 degree, remove agglomerant, sinter, silk-screen LSM cathode and conduct performance test.
Description
Technical field
The present invention relates to the intermediate temperature solid oxide fuel cell anode technology, particularly a kind of flat composite double layer anode amplifying technique that can be used as intermediate temperature solid oxide fuel cell.
Background technology
Solid Oxide Fuel Cell is all solid state electrochemical energy conversion equipment that chemical energy is converted into electric energy, flat solid oxide fuel cell is the research through Dalian Chemiclophysics Inst., Chinese Academy of Sciences in recent years, has developed into to replace conventional thin plate solid electrolyte conduct oxygen ions with the YSZ solid electrolyte film (number of patent application: 99112870.2) working temperature with fuel cell has dropped to 800 ℃ or lower.Though the research of anode of solid oxide fuel cell and preparation have obtained certain progress (number of patent application: 98113759.8), yet to adopt the composite double layer anode area have been 80cm owing to successfully prepare recently in the laboratory
2Above electrode.At the negative electrode effective area is 56cm
2The time, adopt composite double layer anode, with H
2, O
2During for fuel, improved 50% than individual layer commodity NiO-YSZ power output.
Summary of the invention
The purpose of this invention is to provide a kind of solid oxide fuel battery composite double layer anode, i.e. current collection layer and electrochemical reaction active reaction layer, by the technology amplifying technique that roll extrusion unites two into one, composite double layer anode area 80cm
2More than, thickness 0.4-1.5mm.
For achieving the above object, the invention discloses a kind of intermediate temperature solid oxide fuel cell composite double layer anode, form by current collection layer and active electrochemical reaction layer, wherein, by the NiO-YSZ mixture that contains commodity Nio, mix the polyvinyl butyral resin binding agent and constitute current collection layer; The NiO that is decomposed by nickel nitrate mixes with YSZ, mixes the polyvinyl butyral resin binding agent and constitutes active electrochemical reaction layer; Above-mentioned two layers of technology that unites two into one by roll extrusion are made composite double layer anode, and on composite double layer anode, be coated with the YSZ thin film solid electrolyte.
In containing the NiO-YSZ mixture of commodity NiO, commodity NiO content is 30-75 (wt) %, mixes the polyvinyl butyral resin binding agent of 10-40 (wt) %; In the NiO that is decomposed by nickel nitrate and mixture that YSZ mixes, nickel nitrate is 30-80 (wt) % at the NiO of 650-900 ℃ of decomposition content, mixes the polyvinyl butyral resin binding agent of 10-40 (wt) %.
The polyvinyl butyral resin binding agent is by polyvinyl butyral resin, o-phthalic acid dibutyl ester, and n-butanol is formed, and its ratio is o-phthalic acid dibutyl ester 5-30%, polyvinyl butyral resin 5-30%, n-butanol 40-90%.
N-butanol in the polyvinyl butyral resin binder formula also can be used propyl alcohol, isopropyl alcohol or isobutanol.
A kind of preparation method of intermediate temperature solid oxide fuel cell composite double layer anode, its step is in regular turn:
The first step, mix earlier and mix the polyvinyl butyral resin binding agent and be rolled into current collection layer with commodity NiO and yttria-stabilized zirconia (YSZ), after NiO that nickel nitrate is decomposed and YSZ mixing mix the polyvinyl butyral resin binding agent and be rolled into active electrochemical reaction layer; Second step two-layerly united two into one on roller press above-mentioned, was rolled into certain thickness composite double layer anode; The 3rd step, composite double layer anode plated the YSZ thin film solid electrolyte after, 230 ℃-1400 ℃ intensification, remove organic binder bond, sintering, silk screen printing LSM negative electrode carries out fuel battery performance again and tests.The method of wherein said nickel nitrate decomposing N iO is, nickel nitrate is decomposed in tube furnace, heats up with 2-10 ℃/min, and 400 ℃/1-4h, 800 ℃/2-10h decomposes sintering.The preparation method of intermediate temperature solid oxide fuel cell composite double layer anode wherein is to heat up with 2-10 ℃/min speed, and each section temperature retention time is: 200-250 ℃/0.5-2h, 400-450 ℃/0.5-4h, 1000 ℃/0.5-2h, 1400 ℃/1-6h, battery is 650 ℃ of-800 ℃ of runnings.
Employed YSZ solid thin film electrolyte is by the Chinese patent application number 99112870.2 method preparations that provided among the present invention.
Composite double layer used in the present invention three-in-one at the bottom of for anode by the Chinese patent application number 99113329.3 methods preparations that provided.
Embodiment
Embodiment is provided below, and the present invention is further described:
Embodiment 1
The solid oxide fuel battery composite double layer anode preparation.
Take by weighing 30g commodity NiO, 24.2g YSZ, in absolute ethyl alcohol, after the ground and mixed, add that 27.0g polyvinyl butyral resin binding agent (form and formula rate: polyvinyl butyral resin: di-n-octyl phthalate: n-butanol=20: 20: 100) be rolled into the thick anode current of 1.0mm collecting layer by binding agent; Take by weighing the 2.8g nickel nitrate behind 800 ℃/2-6h decomposing N iO, with 2.2g YSZ ground and mixed add that the 2.5g binding agent is rolled into the thick anode active layer of 0.2mm, unite two into one two-layer again, be rolled into the thick composite double layer anode of 1.1mm.
Embodiment 2
The solid oxide fuel cell electrode preparation
Composite double layer anode is plated the 10-20um solid electrolyte film by the technology of the patent No. 991122870.2, heat up 230 ℃/1-2h with 2-10 ℃/min, binding agent is removed in 400 ℃/1-4h heat treatment, 1400 ℃/2-5h sintering is with silk screen printing LSM cathode material, sintering.
Embodiment 3
Solid-oxide fuel battery performance is estimated
In order to compare experiment with composite double layer anode, the fuel cell electrode that also to have prepared simple commodity NiO in addition be substrate, performance test is with H
2, O
2Be fuel, working temperature is 800 ℃, and two kinds of electrode performances see Table 1.As can be seen from Table 1, though both Open Circuit Potential all more than 1 volt, the battery performance power output of composite anode is higher by 50% than individual layer commodity NiO performance
Two kinds of battery performances of table 1. relatively
| Electrode is formed | Composite double layer NiO anode | Individual layer commodity NiO anode |
| Working temperature | 800℃ | 800℃ |
| Open Circuit Potential | 1.07V | 1.07V |
| Peak power output | 15W | 10W |
Claims (7)
1. intermediate temperature solid oxide fuel cell Composite Double anode, form by current collection layer and active electrochemical reaction layer, it is characterized in that, mix by NiO that contains NiO and yttria-stabilized zirconia, the NiO-YSZ mixture is mixed the polyvinyl butyral resin binding agent and is constituted current collector; The NiO that is decomposed by nickel nitrate mixes with YSZ, mixes the polyvinyl butyral resin binding agent and constitutes active electrochemical reaction layer; Above-mentioned two layers of technology that unites two into one by roll extrusion are made composite double layer anode; And on the conversion zone side of composite double layer anode preparation YSZ thin film solid electrolyte.
2. intermediate temperature solid oxide fuel cell composite double layer anode as claimed in claim 1 is characterized in that, in containing the NiO-YSZ mixture of NiO, NiO content is 30-75 (wt) %, mixes the polyvinyl butyral resin binding agent of 10-40 (wt) %; In the NiO that is decomposed by nickel nitrate and mixture that YSZ mixes, nickel nitrate is 30-80 (wt) % at the NiO of 650-900 ℃ of decomposition content, mixes the polyvinyl butyral resin binding agent of 10-40 (wt) %.
3. intermediate temperature solid oxide fuel cell composite double layer anode as claimed in claim 1, it is characterized in that, the polyvinyl butyral resin binding agent is by polyvinyl butyral resin, o-phthalic acid dibutyl ester, n-butanol is formed, its ratio is o-phthalic acid dibutyl ester 5-30%, polyvinyl butyral resin 5-30%, n-butanol 40-90%.
4. intermediate temperature solid oxide fuel cell composite double layer anode as claimed in claim 3 is characterized in that, the n-butanol in the polyvinyl butyral resin binder formula can be used propyl alcohol, isopropyl alcohol or isobutanol.
5. the preparation method of an intermediate temperature solid oxide fuel cell composite double layer anode, its step is in regular turn: the first step, mix with NiO and yttria-stabilized zirconia (YSZ) earlier, mix the polyvinyl butyral resin binding agent and be rolled into current collector, after NiO that nickel nitrate is decomposed and YSZ mix and mix the polyvinyl butyral resin binding agent, be rolled into active electrochemical reaction layer; Second step two-layerly united two into one on roller press above-mentioned, was rolled into composite double layer anode; The 3rd step, composite double layer anode plated the YSZ thin film solid electrolyte after, 230 ℃-1400 ℃ intensification, remove organic binder bond, sintering, silk screen printing LSM negative electrode carries out fuel battery performance again and tests.
6. the preparation method of intermediate temperature solid oxide fuel cell composite double layer anode as claimed in claim 5, the method of wherein said nickel nitrate decomposing N iO is, nickel nitrate is decomposed in tube furnace, heats up with 2-10 ℃/min, 400 ℃/1-4h, 800 ℃/2-10h decomposes sintering.
7. the preparation method of intermediate temperature solid oxide fuel cell composite double layer anode as claimed in claim 5, it is characterized in that: heat up with 2-10 ℃/min speed, each section temperature retention time is: 200-250 ℃/0.5-2h, 400-450 ℃/0.5-4h,, 1000 ℃/0.5-2h,, 1400 ℃/1-6h, battery is 650 ℃ of-800 ℃ of runnings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN02124836A CN1464577A (en) | 2002-06-20 | 2002-06-20 | Moderate temperature solid oxide fuel battery composite double layer anode and process for preparing |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN02124836A CN1464577A (en) | 2002-06-20 | 2002-06-20 | Moderate temperature solid oxide fuel battery composite double layer anode and process for preparing |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100403588C (en) * | 2005-09-14 | 2008-07-16 | 中国科学院过程工程研究所 | Method for producing solid oxide fuel cell anode substrate and die |
| CN101847726A (en) * | 2010-05-31 | 2010-09-29 | 中国科学技术大学 | Composition and method for preparing cathode contact layer of solid oxide fuel battery |
| CN116864704A (en) * | 2023-09-04 | 2023-10-10 | 中石油深圳新能源研究院有限公司 | Anode material of fuel cell, preparation method thereof, fuel cell and anode thereof |
-
2002
- 2002-06-20 CN CN02124836A patent/CN1464577A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100403588C (en) * | 2005-09-14 | 2008-07-16 | 中国科学院过程工程研究所 | Method for producing solid oxide fuel cell anode substrate and die |
| CN101847726A (en) * | 2010-05-31 | 2010-09-29 | 中国科学技术大学 | Composition and method for preparing cathode contact layer of solid oxide fuel battery |
| CN101847726B (en) * | 2010-05-31 | 2014-09-10 | 吉世尔（合肥）能源科技有限公司 | Composition and method for preparing cathode contact layer of solid oxide fuel battery |
| CN116864704A (en) * | 2023-09-04 | 2023-10-10 | 中石油深圳新能源研究院有限公司 | Anode material of fuel cell, preparation method thereof, fuel cell and anode thereof |
| CN116864704B (en) * | 2023-09-04 | 2023-11-24 | 中石油深圳新能源研究院有限公司 | Anode material of fuel cell, preparation method thereof, fuel cell and anode thereof |
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