CN102299354B - Tubular solid oxide fuel cell composite ceramics connector and preparation method thereof - Google Patents
Tubular solid oxide fuel cell composite ceramics connector and preparation method thereof Download PDFInfo
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- CN102299354B CN102299354B CN201010216144.2A CN201010216144A CN102299354B CN 102299354 B CN102299354 B CN 102299354B CN 201010216144 A CN201010216144 A CN 201010216144A CN 102299354 B CN102299354 B CN 102299354B
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The present invention relates to tubular solid oxide fuel cell composite ceramics connector and preparation method thereof, especially anode support tube type solid oxide fuel cell composite ceramics connector and preparation method thereof, belongs to fuel cell material field.Tubular solid oxide fuel cell composite ceramics connector of the present invention, by La doped strontium titanate layer with strontium lanthanum manganese oxide layer is two-layer forms, by the way of slurry brushing, first by La doped strontium titanates slurry brush on anode, the slurry of brushing strontium lanthanum manganese oxide thereon again after drying, then burn altogether with tubular cells anode, fine and close two-layer compound ceramic joining body can be obtained.Present invention process is simple, preparation cost is low, connector is reliable and stable, sound construction, and associativity is good, is conducive to the cost reducing tubular type SOFC battery pile.
Description
Technical field
The present invention relates to tubular solid oxide fuel cell composite ceramics connector and preparation method thereof, especially anode support tube type solid oxide fuel cell composite ceramics connector and preparation method thereof, belongs to fuel cell material field.
Background technology
Fuel cell, as a kind of new energy source technology, has the plurality of advantages such as efficient, clean, safe and reliable.Solid Oxide Fuel Cell (SOFC), except having the Common advantages of the efficient fuel cells such as with environmental friendliness, due to its all solid state characteristic, makes it design more flexibly, more convenient operation and safety and reliability.Because SOFC monocell operating voltage only has about 1V, need in actual applications to utilize connector monocell to be assembled into battery pile to improve its output voltage and power output.Wherein planar SOFC mainly adopts alloy material as connector along with the reduction of working temperature; Tubular type SOFC due to working temperature higher, so ceramic material can only be used as connector.Because connector side is reducing atmosphere, opposite side is oxidizing atmosphere, and therefore metallic interconnect materials will have very high stability; Connector should have higher electronic conductivity under the two atmosphere of oxidationreduction simultaneously, and will have enough densityes to ensure the voltage of battery.But the material meeting these conditions is considerably less simultaneously.
At present, conventional material is the Lanthanum Chromite of doping.It is not only more stable under the dual atmosphere of oxidationreduction, and has higher electronic conductivity.But the major defect of the Lanthanum Chromite of doping is that sintering activity is poor, be very difficult to preparation, therefore have to the preparation method adopted costly.Such as: Siemens-Westinghouse Electric adopts plasma spraying method, wide 11mm, the doping Lanthanum Chromite connector bar of thick 100 μm has been prepared along tube axis direction.But because complex process, cost are higher, be difficult to commercialization always.
Summary of the invention
The object of the invention is to propose a kind of tubular solid oxide fuel cell composite ceramics connector and preparation method thereof, especially anode support tube type solid oxide fuel cell composite ceramics connector and preparation method thereof.
The Solid Oxide Fuel Cell composite ceramics connector that the present invention proposes is by La doped strontium titanate layer and strontium lanthanum manganese oxide layer is two-layer forms.La doped strontium titanate layer consists of La
xsr
1-xtiO
3, wherein, x=0.1 ~ 0.4, thickness is 10 ~ 20 μm; Strontium lanthanum manganese oxide layer consists of La
0.8sr
0.2mnO
3, thickness is 10 ~ 20 μm.
Solid Oxide Fuel Cell composite ceramics connector of the present invention and preparation method thereof, its step is followed successively by:
(1) slurry of La doped strontium titanates slurry and strontium lanthanum manganese oxide is prepared respectively.
The mass fraction of each component of described La doped strontium titanates slurry is: La doped Sr titanate powder 40 parts; The mixed solvent of ethanol and butanone or wherein any one solvent totally 80 ~ 120 parts, binding agent polyvinyl butyral resin (PVB) 1 ~ 4 part; Dispersant triethanolamine (TEA) 1.5 ~ 3.5 parts.
Described La doped Sr titanate powder consists of La
xsr
1-xtiO
3, wherein, x=0.1-0.4;
The mass fraction of each component of described strontium lanthanum manganese oxide slurry is: strontium lanthanum manganese oxide powder 40 parts, the mixed solvent of ethanol and butanone or wherein any one solvent totally 80 ~ 120 parts; Dispersant triethanolamine (TEA) 1.2 ~ 2 parts; Binding agent polyvinyl butyral resin (PVB) 1.2 ~ 2.4 parts; Plasticizer phthalic acid dioctyl ester (DOP) and polyethylene glycol (PEG) or wherein any one totally 2.4 ~ 4 parts.
The chemical formula of described strontium lanthanum manganese oxide is La
0.8sr
0.2mnO
3.
(2) above-mentioned two kinds of slurries are mixed respectively, the air in removing slurry.
Described mixing preferably adopts planetary ball mill to mix 2 ~ 3 hours, and mixing preferably uses ZrO
2mill ball or doping ZrO
2mill ball.ZrO
2mill ball or doping ZrO
2mill ball is usually conventional commercial product, can obtain in commercially available mode.
The preferred rotating speed of described planetary ball mill is 100 ~ 500 revs/min.
Air in described removing slurry is preferably slurry to carry out vacuumizing process 2 ~ 3 minutes.
(3) on anode support tube biscuit, one deck electrolyte slurry is flooded, axially partial electrolyte slurry is wiped along pipe after matter slurry drying to be electrolysed, then squeegeeing step (2) gained La doped strontium titanates slurry on the anode support tube biscuit exposed, after to be dried, continue squeegeeing step (2) gained strontium lanthanum manganese oxide slurry, dry.
The number of times of described brushing preferably 2 ~ 3 times.
Described electrolyte slurry is preferably yttrium stable zirconium oxide or scandium stabilizing zirconia slurry.
(4) step (3) gained biscuit is put into Muffle furnace and is sintered.
Described calcination condition preferably 1300 ~ 1400 DEG C insulation 3 ~ 10 hours.
The invention has the advantages that:
1, technique is simple.Connector can be prepared easily on tubular type SOFC battery by the way of slurry brushing;
2, connector area is controlled.The size of electrolyte area is wiped by changing, can control connection bulk area easily;
3, with low cost.Adopt and the way of anode support tube co-sintering, economical, simple and convenient, be conducive to tubular type SOFC commercialization;
4, sound construction, associativity is good.Owing to being standby by firing altogether, connector is together with anode sintering, and therefore associativity is better, is conducive to improving battery thermal circulation performance;
5, reliable and stable, the life-span is long.Ceramic joining body can not get rusty oxidation, and each layer is Stability Analysis of Structures in corresponding atmosphere.
Accompanying drawing explanation
Fig. 1 is the SEM photo of the connector section of embodiment 1;
Fig. 2 is embodiment 2 tubular type monocell discharge performance curve at different temperatures;
Illustrate: this figure is two ordinates, and the left side is I-V curve, and namely the current value of every bit obtains corresponding power to the product of magnitude of voltage, thus draws the current-power density curve on the right.
Fig. 3 is the impedance spectrogram of embodiment 2 tubular type monocell at different temperatures between connector and anode;
Illustrate: ordinate is polarization impedance, abscissa is ohmage.All resistance values are all multiplied by area, obtain surface resistance value.
Fig. 4 is the tubular type monocell of embodiment 3 with connector discharge performance curve at different temperatures;
Fig. 5 is embodiment 4 two tubular type SOFC series-connected cell heaps discharge performance curves at different temperatures.
Embodiment
Embodiment 1: the preparation of tubular type SOFC two-layer compound ceramic joining body
The present invention's La doped Sr titanate powder used is synthesized by solid reaction process.Raise from 0.1 along with La doping 0.4, the conductivity of material also improves gradually.But be above 0.4 and there will be second-phase.Therefore the preferred La doping of embodiments of the invention is the powder (La of 0.4
0.4sr
0.6tiO
3) as research object.La
0.8sr
0.2mnO
3powder is commercially available powder.
Get La doped strontium titanates (La
0.4sr
0.6tiO
3) powder 44 grams, ethanol 100 grams, TEA1.5 gram, add 200 grams, zirconium oxide abrasive ball, on planetary ball mill, ball milling 1 hour, then adds PVB2 gram in above-mentioned slurry, continue ball milling 2 hours, then vacuumize process 2 ~ 3 minutes, remove the air in slurry, obtain La doped strontium titanates and be coated with slurry.
Get strontium lanthanum manganese oxide (La
0.8sr
0.2mnO
3) powder 20 grams, butanone 20 grams, alcohol 10 grams, TEA0.6 gram, add 60 grams of zirconium oxide abrasive balls, on planetary ball mill, ball milling 1 hour, then adds PVB0.6 gram in above-mentioned slurry, DOP0.6 gram, PEG0.6 gram, continues ball milling 2 hours, then vacuumizes process 2 ~ 3 minutes, remove the air in slurry, obtain strontium lanthanum manganese oxide and be coated with slurry.
Anode support tube biscuit floods one deck electrolyte (thickness is about tens microns), after its drying, wipes partial electrolyte with cotton swab, (area is about 2cm to make anode expose the rectangular region of a slice
2), then with writing brush by La
0.4sr
0.6tiO
3slurry brushing at this bar-shaped zone, and extremely must be covered whole strip region by slurry brushing completely.Treat the La on pipe
0.4sr
0.6tiO
3after slurry drying, continue to brush La thereon
0.8sr
0.2mnO
3slurry, and put into oven drying.Then tubular type SOFC biscuit is put into Muffle furnace to sinter.Anode support tube, electrolyte and connector burn 3 hours altogether at 1400 DEG C.
As can be seen from Figure 1, La
0.4sr
0.6tiO
3thickness is about 20 microns, La
0.8sr
0.2mnO
3thickness is about 15 microns.This is two-layer all dense, and combines better.Illustrate that the way that this two-layer compound connector and anode support tube biscuit burn altogether is feasible.
Embodiment 2: the performance test of tubular type monocell and connector performance characterization
According to tubular type monocell prepared by embodiment 1, the experiment condition of its power generation performance test is:
Cathode area: 11cm
2(thickness about 50 ~ 60 microns);
Connector area: 2.5cm
2; Thickness about 35 microns of (La
0.4sr
0.6tiO
3about 20 microns, La
0.8sr
0.2mnO
3about 15 microns);
Test gas: H
2, O
2, unsealing.H
2flow is 100ml/min, O
2flow is 80ml/min.
Experimental result as shown in Figure 2.Under 900 DEG C of conditions, the maximum power density of battery can reach 140mW/cm
2, the total power output of monocell can reach about 1.5 watts.
Connector leads to material as Electricity Federation, and its resistance is the smaller the better in theory.As can be seen from Figure 3, at 900 DEG C, 850 DEG C and 800 DEG C, the ohmage between connector and anode is respectively 0.2 Ω cm
2, 0.26 Ω cm
2with 0.34 Ω cm
2.Ohmage between connector and anode reduces significantly along with the rising of temperature, shows ceramic joining body and at high temperature more has advantage.
Embodiment 3: junctional complex thickness proportion is on the impact of battery performance
Connector preparation method is similar to Example 1.Difference is that the brushing of La doped strontium titanates slurry is thinner, and the brushing of strontium lanthanum manganese oxide slurry is thicker.The experiment condition of power generation performance test is:
Cathode area: 10.12cm
2(thickness about 50 ~ 60 microns);
Connector area: 2.25cm
2; Thickness about 35 microns of (La
0.4sr
0.6tiO
3about 15 microns, La
0.8sr
0.2mnO
3about 20 microns);
Test gas: H
2, O
2, unsealing.H
2flow is 100ml/min, O
2flow is 80ml/min.
Experimental result as shown in Figure 4.Monocell is when running for 900 DEG C, and maximum power density is about 160mW/cm
2.Battery performance is relative to embodiment 2 (140mW/cm
2) improve.Reason is: relative to the former, and the connector structure of the present embodiment has carried out certain optimization.Namely under the substantially constant prerequisite of connector general thickness, La doped strontium titanate layer thickness reduces, and strontium lanthanum manganese oxide layer thickness increases.Because La doped strontium titanates conductivity is lower, strontium lanthanum manganese oxide conductivity is higher, so the resistance decreasing of connector, the power output of battery increases.
Embodiment 4: two tubular type SOFC series-connected cell pile power generating experiments
Two tubular type SOFC features are as follows:
Battery 1: have connector, cathode area: 10.12cm
2, connector area: 2.25cm
2; The preparation method of connector is with embodiment 1.
Battery 2: without connector, cathode area is about 12cm
2.
Generator experimental condition: H
2, O
2, unsealing.H
2flow is 200ml/min, O
2flow is 160ml/min.
Serial battery implementation method:
The cathode surface of battery 1 and battery 2 draws platinum grid, and is used for collected current with platinum guaze parcel.The negative electrode platinum guaze of battery 1 draws two platinum filaments, and another root of galvanization surveys voltage.The pipe inner anode of battery 2 adds nickel felt and receives electricity, and draws two platinum filaments on nickel felt.The connector of battery 1 is fixed a fritter platinum guaze, and contacts with the negative electrode platinum guaze of battery 2, then with nickel filament by two tubular cells side by side, parallel binding well.Stack current loop is followed successively by: battery 1 negative electrode, external circuit, battery 2 anode, battery 2 electrolyte, battery 2 negative electrode, battery 1 connector, battery 1 anode, battery 1 electrolyte, battery 1 negative electrode.
As can be seen from Figure 5, at 800 DEG C, 850 DEG C and 900 DEG C, the open circuit voltage of battery pile is about about 2.2V, is two monocell open circuit voltage sums.Illustrate that serial battery is successful.900 DEG C time, two tubular cells peak power outputs are 2.2 watts.
Claims (7)
1. the tubular solid oxide fuel cell preparation method of composite ceramics connector, described tubular solid oxide fuel cell composite ceramics connector is by La doped strontium titanate layer and strontium lanthanum manganese oxide layer is two-layer forms, and La doped strontium titanate layer consists of La
xsr
1-xtiO
3, wherein, x=0.1 ~ 0.4, thickness is 10 ~ 20 μm; Strontium lanthanum manganese oxide layer consists of La
0.8sr
0.2mnO
3, thickness is 10 ~ 20 μm, comprises the steps:
(1) slurry of La doped strontium titanates slurry and strontium lanthanum manganese oxide is prepared respectively:
The mass fraction of each component of described La doped strontium titanates slurry is: La doped Sr titanate powder 40 parts; The mixed solvent of ethanol and butanone or wherein any one solvent totally 80 ~ 120 parts, binding agent polyvinyl butyral resin (PVB) 1 ~ 4 part; Dispersant triethanolamine (TEA) 1.5 ~ 3.5 parts;
Described La doped Sr titanate powder consists of La
xsr
1-xtiO
3, wherein, x=0.1-0.4;
The mass fraction of each component of described strontium lanthanum manganese oxide slurry is: strontium lanthanum manganese oxide powder 40 parts, the mixed solvent of ethanol and butanone or wherein any one solvent totally 80 ~ 120 parts; Dispersant triethanolamine 1.2 ~ 2 parts; Binding agent polyvinyl butyral resin 1.2 ~ 2.4 parts; Plasticizer phthalic acid dioctyl ester and polyethylene glycol or wherein any one totally 2.4 ~ 4 parts;
The chemical formula of described strontium lanthanum manganese oxide is La
0.8sr
0.2mnO
3;
(2) above-mentioned two kinds of slurries are mixed respectively, the air in removing slurry;
(3) on anode support tube biscuit, one deck electrolyte slurry is flooded, axially partial electrolyte slurry is wiped along pipe after matter slurry drying to be electrolysed, then squeegeeing step (2) gained La doped strontium titanates slurry on the anode support tube biscuit exposed, after to be dried, continue squeegeeing step (2) gained strontium lanthanum manganese oxide slurry, dry;
(4) step (3) gained biscuit is put into Muffle furnace and is sintered, and sintering condition is 1300 ~ 1400 DEG C of insulations 3 ~ 10 hours.
2. by the preparation method of tubular solid oxide fuel cell composite ceramics connector according to claim 1, it is characterized in that, in described step (2), incorporation time is 2 ~ 3 hours.
3. by the tubular solid oxide fuel cell preparation method of composite ceramics connector described in claim 1 or 2, it is characterized in that, in described step (2), be mixed into planetary ball mill mixing.
4., by the preparation method of tubular solid oxide fuel cell composite ceramics connector according to claim 3, it is characterized in that, described planetary ball mill rotating speed is 100 ~ 500 revs/min.
5. by the preparation method of tubular solid oxide fuel cell composite ceramics connector according to claim 1, it is characterized in that, in described step (2), in removing slurry, the method for air is that slurry carries out vacuumizing process 2 ~ 3 minutes.
6. by the preparation method of tubular solid oxide fuel cell composite ceramics connector according to claim 1, it is characterized in that, in described step (3), the number of times of brushing is 2 ~ 3 times.
7., by the preparation method of tubular solid oxide fuel cell composite ceramics connector according to claim 1, it is characterized in that, described step (3) electrolyte slurry is yttrium stable zirconium oxide or scandium stabilizing zirconia slurry.
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|---|---|---|---|
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|---|---|---|---|
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|---|---|---|---|---|
| CN104064786B (en) * | 2014-07-17 | 2016-08-17 | 中国科学院上海硅酸盐研究所 | A kind of preparation method of cathode of solid oxide fuel cell collector |
| CN108054394B (en) * | 2017-12-07 | 2020-03-31 | 北京理工大学 | Synthetic method of strontium titanate-based material for solid oxide fuel cell |
| CN108023096A (en) * | 2017-12-07 | 2018-05-11 | 北京理工大学 | The preparation method of solid oxide fuel cell densification double-layer ceramic connector |
| CN114944498A (en) * | 2022-05-26 | 2022-08-26 | 西安交通大学 | Integrated connector supported electric symbiotic solid oxide fuel cell/cell stack reactor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314724A (en) * | 2001-04-20 | 2001-09-26 | 中国科学院上海硅酸盐研究所 | Composite connection board for solid oxide fuel cell stack and its producing method |
| CN101075681A (en) * | 2006-05-19 | 2007-11-21 | 合肥学院 | Method for producing solid oxide fuel cell connecting board at 500-800 degree moderate temperature |
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2010
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314724A (en) * | 2001-04-20 | 2001-09-26 | 中国科学院上海硅酸盐研究所 | Composite connection board for solid oxide fuel cell stack and its producing method |
| CN101075681A (en) * | 2006-05-19 | 2007-11-21 | 合肥学院 | Method for producing solid oxide fuel cell connecting board at 500-800 degree moderate temperature |
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