CN102651480A - Anode-supported solid oxide fuel cell, cell stack and preparation method thereof - Google Patents
Anode-supported solid oxide fuel cell, cell stack and preparation method thereof Download PDFInfo
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- CN102651480A CN102651480A CN2011100450476A CN201110045047A CN102651480A CN 102651480 A CN102651480 A CN 102651480A CN 2011100450476 A CN2011100450476 A CN 2011100450476A CN 201110045047 A CN201110045047 A CN 201110045047A CN 102651480 A CN102651480 A CN 102651480A
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Abstract
The invention relates to an anode-supported solid oxide fuel cell, a cell stack and a preparation method thereof, which belong to the field of fuel cell materials. The anode-supported tubular solid oxide fuel cell comprises an anode support tube with one end sealed, wherein a bar-shaped ceramic connector layer is arranged on the outer side surface of the anode support tube; a compact electrolyte layer is arranged at the part of the outer surface of the anode support tube without the ceramic connector layer, and the compact electrolyte layer and the bar-shaped ceramic connector layer are adjacent to each other and completely cover the outer surface of the anode outer surface; the anode support tube, the compact electrolyte layer and the ceramic connector layer are integrated through cofiring; and a cathode layer is further arranged outside the compact electrolyte layer and disconnected with the ceramic connector layer. The anode-supported solid oxide fuel cell is easy for stacking and has high operating temperature and generating efficiency; a connector is stable and reliable and has a long service life; as the connector and the anode support tube biscuit are prepared through cofiring, convenience and low cost are realized; and meanwhile, the cell structure with one end sealed achieves internal reforming of fuel, compact structure and high power density are also realized.
Description
Technical field
The present invention relates to SOFC of a kind of anode-supported and preparation method thereof, be applicable to tubular type SOFC battery pile, belong to the fuel cell material field.
Background technology
Fuel cell is as a kind of new-generation technology, has efficient, cleaning, plurality of advantages such as safe and reliable.SOFC (SOFC) is except the common advantage with fuel cells such as efficient and environmental friendliness, because its all solid state characteristic makes its design more flexible, more convenient operation and safety and reliability.Advantages such as tubular type SOFC has the elevated-temperature seal of need not, and the anti-thermal shock ability is strong receive widely and paying close attention to.Because SOFC monocell operating voltage has only about 1V, in practical application, need utilize connector that monocell is assembled into battery pile to improve its output voltage and power.Wherein flat SOFC adopts pottery or the alloy connecting plate that has air drain, realizes the collection of electric current easily.Tubular type SOFC is an arcuate structure because of its outside, and electric current collection is difficulty relatively.The cathode support tubular type battery of the one end sealing of US Westinghouse company's research and development; Adopt chemical vapour deposition technique or plasma spraying method to prepare chromic acid lanthanum base pottery connector in an electrolytical side; Realize the connection in series-parallel between the tubular type battery, and reached the very high battery pile life-span.But the above-mentioned battery structure preparation cost of US Westinghouse company's research and development is too high, is difficult to commercialization.
U.S. Accumentric company, Dalian Inst of Chemicophysics, Chinese Academy of Sciences etc. study the tubular type SOFC of anode-supported in succession, but do not see report as yet about the making of its ceramic connector.The path is very long vertically owing to tubular type SOFC, if electric current take out vertically certainly will cause voltage drop that great internal resistance causes and energy loss, and therefore can to shorten the connector design of current path very necessary and urgent in research and development.Because the SOFC working temperature is high, a side is a reducing atmosphere and opposite side is an oxidizing atmosphere, thus the stability of metallic interconnect materials there is very high requirement, so be necessary to use ceramic material as connector.Connector should have higher electronic conductivity under the two atmosphere of OR simultaneously, and enough densityes will be arranged to guarantee the voltage of battery.The material that satisfies these conditions simultaneously is considerably less.Material commonly used is the chromic acid lanthanum that mixes, but the major defect of the chromic acid lanthanum that mixes is that sintering activity is poor, is very difficult to preparation, therefore has to adopt relatively more expensive preparation method (adopting plasma spraying method such as aforementioned Westinghouse Electric).Because of its cost is high, be difficult to commercialization always.
Summary of the invention
The present invention is directed to difficult, the problems such as battery structure is insecure, poor stability, preparation cost height of tubular solid oxide fuel cell in the prior art (SOFC) electric current collection, a kind of anode-supported tubular type solid oxide fuel monocell, battery pile and preparation method thereof are provided.
Anode-supported tubular type SOFC of the present invention (SOFC); The anode support tube that comprises end sealing; The outer surface of said anode support tube is provided with strip pottery connector layer; Said strip pottery connector layer is parallel to the tubular axis of anode support tube, extend to openend from the blind end of the lateral surface of anode support tube, and length is no longer than anode support tube; The part of not establishing ceramic connector layer on the said anode-supported tube outer surface is provided with dense electrolyte layer, and said dense electrolyte layer and strip pottery connector layer adjoin and cover fully the outer surface of anode support tube each other; Said anode support tube, dense electrolyte layer and ceramic connector layer burn altogether and are one; The dense electrolyte layer of said anode support tube lateral surface also is provided with cathode layer outward, and cathode layer does not link to each other with ceramic connector layer.
Said anode-supported thickness of pipe wall is 0.6～1.2mm, and the dielectric substrate thickness is 10～40 μ m, and ceramic connector tunic is thick to be 30～60 μ m.
Further, said anode support tube comprises passive supporting layer, and said supporting layer also is coated with one or more layers electrochemical function layer outward.
The material of said passive supporting layer is the compound of the stable zirconia of nickel oxide and yttrium (the mole doping of yttrium is 3%～8%), the quality percentage composition of nickel oxide in the said composite material, as be 40%～60%; The material of said one or more layers electrochemical function layer is that the stable zirconia of nickel oxide and scandium is (like Zr
0.89Sc
0.1Ce
0.01O
2) compound or nickel oxide and gadolinium doping of cerium oxide (like Ce
0.8Gd
0.2O
1.9) compound or nickel oxide and samarium doping of cerium oxide (like Ce
0.8Sm
0.2O
1.9) compound.Stable zirconia, gadolinium doping of cerium oxide and the samarium doping of cerium oxide of said scandium is conventional material of the prior art, and the quality percentage composition of nickel oxide in each composite material, as is 40%～60%.
Further, said dielectric substrate is selected from the stable zirconia (ScSZ) of the stable zirconia of yttrium (YSZ) layer (the mole doping of yttrium is 8%), scandium layer (like Zr
0.89Sc
0.1Ce
0.01O
2), gadolinium doping of cerium oxide (GDC) layer is (like Ce
0.8Gd
0.2O
1.9), samarium doping of cerium oxide (SDC) layer is (like Ce
0.8Sm
0.2O
1.9), gallic acid strontium lanthanum (LSGM) layer is (like La
0.8Sr
0.2Ga
0.8Mg
0.2O
3) in a kind of or at least two kinds composite bed among them.Stable stable zirconia (ScSZ), gadolinium doping of cerium oxide (GDC), samarium doping of cerium oxide (SDC) and the gallic acid strontium lanthanum (LSGM) of zirconia (YSZ), scandium of said yttrium is conventional material of the prior art.
Further, said ceramic connector layer is stable under pyro-oxidation-reduction atmosphere by doping chromic acid lanthanum, strontium titanate doping, iron-based alloy etc., and the material that has than highly electron conductive and electron transfer number constitutes; Said ceramic connector layer is connector individual layer or connector composite bed.
Said connector individual layer is like the connector individual layer of doping chromic acid lanthanum material formation; Said connector composite bed is like the connector individual layer of doped strontium titanate material and the formed composite bed of connector individual layer of iron-based alloy material.Wherein, doping chromic acid lanthanum such as La
0.7Ca
0.3Cr
0.9Zn
0.05O
3, strontium titanate doping such as La
0.4Sr
0.6TiO
3, iron-based alloy such as La
0.8Sr
0.2MnO
3
The material of said cathode layer is the composite material of the stable zirconia (ScSZ) of iron-based alloy and scandium; Wherein, the lanthanum manganate (La of iron-based alloy such as strontium doping
1-xSr
xMnO
3), further x=0.2, i.e. La
0.8Sr
0.2MnO
3ScSZ consists of Zr
0.89Sc
0.1Ce
0.01O
2The zirconic mass ratio that the lanthanum manganate of said strontium doping and scandium are stable, as be 70: 30.
The said strip pottery connector layer of being located at the lateral surface of anode support tube and being parallel to tubular axis; Be used for the electric current collection on the anode-supported body outside pipe; Be convenient to contact with the negative electrode of adjacent anode-supported tubular type SOFC; Realize the connection in series-parallel between the tubular type battery, constitute battery pile.
With respect to the SOFC of cathode support, anode-supported tubular type SOFC of the present invention has characteristics such as sintering temperature is higher, battery strength is bigger.The raising of sintering temperature helps realizing that ceramic connector and tubular anode biscuit burn altogether, thereby reduces the preparation cost of connector.And the big advantage of intensity can guarantee the stability of SOFC battery of the present invention in operation or thermal cycle process.Can also can improve the concentration of fuel gas through make encapsulation process (as with elevated-temperature seal glass capsulation or filling part asbestos etc.) slightly at the anode support tube openend, thereby improve the performance of battery.
Anode-supported tubular type SOFC of the present invention; The anode tube that adopts end sealing is as supporter; Can on the tube wall of the interior pipe that leads to fuel gas, catalyst be set easily, realize the interior reformation of fuel, realize compact structure and high power density.The catalyst of said realization fuel reforming, like cerium oxide, platinum, ruthenium etc.
Anode-supported tubular type preparation of solid oxide fuel cell of the present invention comprises the steps:
1) with outer surface dipping one deck dielectric substrate of the anode support tube biscuit of end sealing, treat the dielectric substrate drying after, along anode support tube axially wipe the part electrolyte, make the outer surface of anode support tube biscuit expose a continuous rectangular zone;
2) one or more layers ceramic connector slurry of brushing on the stripe region of step 1) gained, treat ceramic connector slurry drying after, put into altogether burning of Muffle furnace, obtain being sintered to anode support, dielectric substrate and the connector layer of one.
3) ceramic connector and the part electrolyte area adjacent with ceramic connector are covered with adhesive tape fully; With the exposed compound impregnated cathode slurry of electrolyte area; After treating the cathode slurry drying, put into Muffle furnace and heat-treat, obtain said anode-supported tubular type SOFC.
In the step 1), the anode support tube biscuit of said end sealing adopts method preparations such as dipping heavy slurry method, slip casting or extrusion moulding, can wipe the size of electrolyte area through change, controls the area of ceramic connector.
Said dipping sinks slurry method, slip casting and extrusion moulding and is in the prior art conventional preparation method; Wherein flood heavy slurry method; But list of references R.Z.Liu, S.R.Wang et al.Dip-coating and co-sintering technologiesfor fabricating tubular solid oxide fuel cells.J Solid State Electrochem (2009) 13:1905-1911; Extrusion moulding; But list of references T.Jardiel; B.Levenfeld; R.Jime ' nez, A.Va ' rez.Fabrication of 8-YSZthin-wall tubes by powder extrusion moulding for SOFC electrolytes.Ceramics International 35 (2009) 2329-2335; Or document Nicolas Droushiotis, Mohd Hafiz Dzarfan Othman et al.Novelco-extruded electrolyte-anode hollow fibres for solid oxide fuel cells.ElectrochemistryCommunications 11 (2009) 1799-1802.
Step 2) in, must the slurry brushing extremely be covered whole strip region fully, otherwise anode and electrolytical edge are prone to cause gas leakage, and then reduce the open circuit voltage of battery;
Step 2) in, said temperature of burning altogether is 1300～1400 ℃, temperature retention time 3～10 hours; Anode-supported thickness of pipe wall after the said burning altogether is 0.6～1.2mm, and the thickness of dielectric substrate is 10 μ m～40 μ m, and the connector layer thickness is 30 μ m～60 μ m.
In the step 3), the stable zirconic mass ratio of strontium lanthanum manganese oxide and scandium is as being 70: 30 in the composite cathode slurry; The heat treated temperature of negative electrode is as being 1200 ℃, and the time is 3～5 hours; Cathode layer thickness is 30～60 μ m.Before the impregnated cathode slurry, cover ceramic connector bar and the part electrolyte area adjacent fully with adhesive tape earlier, with the dipping of isolated cathode slurry with connector; The blank electrolysis matter zone that covers is as the usefulness of the insulation between connector and the negative electrode.
Anode-supported tubular type SOFC of the present invention is when carrying out work, and the interior pipe of logical fuel gas adopts conductive metallic material (ferritic stainless steel such as SUS430, crofer22 APU etc.) or ceramic material (like La
0.7Ca
0.15Sr
0.15O
3), filled and process nickel between the inwall of itself and anode support tube is drawn the electric current on the anode support through breather pipe, thereby can significantly reduce the resistance of electric current collection.The difference of while based on fuel kind; Film on the tube wall that can in above-mentioned ventilation, manage reforming catalyst is set; Utilize the used heat that produces when battery operated to realize the inside reforming (like the inside reforming of methane) of hydrocarbon fuels, thereby reach compact and effect cheaply.Said being restructured as the big molecular conversion that is difficult for diffusion for being prone to the micromolecule of diffusion, like ethanol (C
2H
5OH) can change H into through reforming
2And CO; And H
2Can diffuse to the three phase boundary place rapidly and electrochemical reaction takes place with CO and discharge electronics.
The battery pile of anode-supported tubular type SOFC of the present invention; For a plurality of said anode-supported tubular type SOFCs are in series; Being specially the ceramic connector that the first anode is supported tubular solid oxide fuel cell is connected with the negative electrode that second plate supports tubular solid oxide fuel cell; The ceramic connector that second plate is supported tubular solid oxide fuel cell is connected with the negative electrode that third anode supports tubular solid oxide fuel cell; And by that analogy, be connected together in series, decide according to the required number of series connection.
Advantage of the present invention is following:
1, the electric current collection path is short, power loss is little.The principle concept figure of electric current collection of the present invention is as shown in Figure 1; Anode-supported tubular type SOFC of the present invention is through being arranged on connector the side of anode support tube; With sense of current from changing into vertically along the circumferential direction; Shorten current path greatly, reduced the internal resistance of electric current collection;
2, compact conformation, can realize the inside reforming of fuel.Film on the tube wall that the present invention can manage in ventilation reforming catalyst is set; Realize the inside reforming of hydrocarbon fuels (like methane); The interior reformation principle concept figure of fuel of the present invention is as shown in Figure 2, thereby omits external reformer, reaches compact and effect cheaply.
3, generating efficiency is high.Internal loss is few when reducing internal resistance and meaning generating, utilizes the used heat that produces when battery operated in interior reformation simultaneously, has improved the utilization ratio of used heat, and consequently whole energy utilization efficiency is improved.
4, the connector area is controlled.Wipe the size of electrolyte area, control connection bulk area at an easy rate through change;
5, with low cost.Employing prepares connector with the way of anode support tube co-sintering, and is economical, simple and convenient, helps tubular type SOFC commercialization;
6, sound construction, associativity is good.Owing to be to be equipped with through firing altogether, connector and anode sintering together, so associativity is better, helps improving the battery thermal circulation performance;
7, reliable and stable, the life-span is long.The oxidation of can not getting rusty of pottery connector, each layer be Stability Analysis of Structures in corresponding atmosphere.
In a word, anode-supported tubular type solid oxide fuel cell stack heap of the present invention easily, working temperature is high, generating efficiency is high; Connector is reliable and stable, the life-span is long; Because connector and anode support tube biscuit are fired fully altogether and are formed, and do not increase additional process, can comparatively make things convenient for, prepare economically connector.Simultaneously, the battery structure of end sealing can be realized the interior reformation of fuel, compact conformation, and power density is high.
Description of drawings
Fig. 1 is the concept map of electric current collection principle of the present invention;
Among the figure, 1 anode support tube; 2 dielectric substrates; 3 ceramic connector layers; 4 cathode layers; 5 insulation layers; Current direction on 6 anode support tubes; Electric current output on 7 connectors.
Fig. 2 is the interior reformation principle concept figure of fuel of the present invention;
Among the figure, 8 fuel gas streams to; 9 preheating reformer tubes; 10 catalyst.
Fig. 3 is that embodiment 2 is with H
2The performance test figure of tubular type SOFC monocell under different temperatures for fuel;
This figure is two Y coordinates.The left side is a current-voltage curve; The right is corresponding electric current-power density curve.
Fig. 4 is the performance test figure of tubular type SOFC monocell under different temperatures of fuel for embodiment 3 with ethanol;
Fig. 5 piles up the performance test figure under the different temperatures for two tubular type SOFC series-connected cells of embodiment 4.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment, should be understood that these embodiment only are used to the present invention is described and are not used in restriction protection scope of the present invention.
The preparation of tubular type SOFC monocell may further comprise the steps:
1, the preparation of double-layer ceramic connector slurry:
At first, adopt solid reaction process to prepare some lanthanum strontium titanate doping (La
0.4Sr
0.6TiO
3) powder.Strontium lanthanum manganese oxide (La
0.8Sr
0.2MnO
3) powder is the product of commercially available U.S. Fuel Cell Materials Corporation company.Get lanthanum strontium titanate doping powder 44 grams earlier, absolute ethyl alcohol 100 grams, triethanolamine 1.5 grams; Add zirconium oxide abrasive ball 200 grams, ball milling is 1 hour on planetary ball mill, adds PVB (Pioloform, polyvinyl acetal) 1 gram then; Continued ball milling 2 hours; Vacuumize then and handled 2～3 minutes, remove the air in the slurry, obtain the lanthanum strontium titanate doping and be coated with slurry.
Get strontium lanthanum manganese oxide (La
0.8Sr
0.2MnO
3) powder 20 grams, butanone 20 grams, ethanol 10 grams, triethanolamine 0.6 gram; Add 60 gram zirconium oxide abrasive balls, ball milling is 1 hour on planetary ball mill, adds PVB 0.6 gram then; Dibutyl phthalate 0.6 gram, polyethylene glycol 0.6 gram continued ball milling 2 hours; Vacuumize then and handled 2～3 minutes, remove the air in the slurry, obtain strontium lanthanum manganese oxide and be coated with slurry.
2, the preparation of the tubular type SOFC monocell of anode-supported
Dipping one deck electrolyte slurry (thickness is about 25 μ m) on the anode support tube biscuit, said electrolytical material is scandium doped zirconia (SSZ:Zr
0.89Sc
0.1Ce
0.01O
2), treat it and wipe the part electrolyte with cotton swab after dry that (area is about 2cm to make anode expose the rectangular zone of a slice
2), then with writing brush with La
0.4Sr
0.6TiO
3The slurry brushing is at this bar-shaped zone, and must be with the slurry brushing to covering whole strip region fully, otherwise anode and electrolytical edge be prone to cause leak gas, and this can reduce the open circuit voltage of battery.Treat the La on the pipe
0.4Sr
0.6TiO
3Behind the slurry drying, continue to brush La above that
0.8Sr
0.2MnO
3Slurry, and put into oven drying.Then tubular type SOFC biscuit being put into Muffle furnace calcines.Anode support tube, electrolyte and connector burnt 3 hours at 1400 ℃ altogether.
Ceramic connector and the part electrolyte area adjacent with ceramic connector are covered with adhesive tape fully; With exposed electrolyte area dipping composite cathode slurry; Wherein the composite cathode slurry is that 70: 30 strontium lanthanum manganese oxide of mass ratio is mixed with the stable zirconia of scandium, and the mixed solvent (mass ratio is 1: 2) that adds alcohol and butanone is processed slurry; After treating the cathode slurry drying, put into Muffle furnace and heat-treat, heat treated temperature is 1200 ℃, and the time is 3 hours; Obtain the tubular type SOFC monocell (anode-supported tubular type SOFC) of embodiment 1.
Through detecting the tubular type SOFC monocell of present embodiment 1 gained, its anode-supported thickness of pipe wall is 1.2mm, and the dielectric substrate thickness is 15 μ m, and ceramic connector tunic is thick to be 30 μ m; The thickness of cathode layer is 40 μ m.
Embodiment 2
With H
2Tubular type SOFC monocell performance test for fuel
According to the tubular type monocell of embodiment 1 preparation, the experiment condition of its power generation performance test is: cathode area: 9cm
2Test gas: H
2, O
2, unsealing.H
2Flow is 100ml/min, O
2Flow is 80ml/min.
Method of testing is a four-terminal method.Utilize constant-current source to connect,, draw current-voltage curve (I-V curve) through changing the way of testing current voltage with battery.Then a certain current value multiply by the correspondent voltage value, obtain the power (power can obtain power density divided by cathode area) under this electric current.Can obtain electric current-power density curve (I-P curve) like this.As shown in Figure 3.Fig. 3 representes battery I-V and I-P curve of (900 ℃, 850 ℃, 800 ℃ and 750 ℃) under different temperatures.Wherein, open circuit is a little less than 1V, and this is because due to the influence of the used constant-current source of experiment.Because this constant-current source self-resistance is less, even and under the situation that does not have to open circuit still can connect, form the loop of certain electric current, thereby cause open circuit to decrease.As can beappreciated from fig. 3, battery performance is along with the rising of temperature is significantly increased.In the time of 900 ℃, the battery maximum power density is about 550mW/cm
2, realized better power output.
With ethanol is the tubular type SOFC monocell performance test of fuel
SOFC is that its fuel tolerance is strong with respect to a big advantage of the fuel cell of other types, can directly be fuel with the hydrocarbon.This is that hydrocarbon fuel can be by direct oxidation, perhaps in inside battery generation reforming reaction at anode because the SOFC working temperature is higher.The contingent reforming reaction of alcohol and steam is following:
C
2H
5OH+H
2O→2CO+4H
2
C
2H
5OH+3H
2O→2CO
2+6H
2
CO+H
2O→CO
2+H
2
Tubular type SOFC monocell preparation method is with embodiment 1, and interior breather pipe adopts the nickel plating stainless steel tube during performance test, utilizes alcohol/H
2Reform in O mixing material (volume ratio is 2: the 1) vaporization and generate electricity.Alcohol/H
2O solution places 70 ℃ of waters bath with thermostatic control to heat, with N
2For carrier gas is blown into anode surface with it.The cathode area of monocell is about 10cm
2
Experimental result is as shown in Figure 4.In the time of 900 ℃, battery peak power output density is about 400mW/cm
2This numerical value is relatively with H
2For the test result of fuel, to hang down.This is that diffusion velocity compares H because the molecular weight ratio of ethanol is bigger
2Slowly, cause the polarization impedance of battery bigger, so performance descend to some extent.But, because H is compared in the alcohol source
2Extensively, and storing and transport more convenient, is that fuel still has bigger prospect with alcohol therefore.
Embodiment 4
Two tubular type SOFC series-connected cell pile power generating experiments
Two tubular type SOFC are tied up side by side, realize the series connection generating.Two tubular type SOFC characteristics are following:
Battery 1: connector is arranged, cathode area: 10.12cm
2, connector area: 2.25cm
2The preparation method of connector is with embodiment 1.
Battery 2: no connector, the about 12cm of cathode area
2
Generator experimental condition: H
2, O
2, unsealing.H
2Flow is 200ml/min, O
2Flow is 160ml/min.
Battery series connection implementation method:
The cathode surface of battery 1 and battery 2 is drawn the platinum grid, and is used for collected current with the platinum guaze parcel.Draw two platinum filaments on the negative electrode platinum guaze of battery 1, another root of galvanization is surveyed voltage.The pipe inner anode of battery 2 adds the nickel felt and receives electricity, and on the nickel felt, draws two platinum filaments.A fixing fritter platinum guaze on the connector of battery 1, and contact with the negative electrode platinum guaze of battery 2, then with nickel filament with two tubular type batteries side by side, parallel binding well.The stack current loop is followed successively by:
Battery 1 negative electrode, external circuit, battery 2 anodes, battery 2 electrolyte, battery 2 negative electrodes, battery 1 connector, battery 1 anode, battery 1 electrolyte,
Battery 1 negative electrode
Experimental result is as shown in Figure 5.As can be seen from the figure, under 800 ℃ and 850 ℃, the open circuit voltage of battery pile all more than 2V, equals two monocell open circuit voltage sums basically, explains that the battery series connection is successful.Thereby make feasibility of the present invention obtain checking.When 800 ℃ and 850 ℃, the battery pile peak power output is respectively 2.5W and 3.2W.
Embodiment 5
The preparation of tubular type SOFC monocell may further comprise the steps:
1, the preparation of double-layer ceramic connector slurry:
Get lanthanum strontium titanate doping (La
0.4Sr
0.6TiO
3) powder 44 grams, absolute ethyl alcohol 100 grams, triethanolamine 1.5 grams; Add zirconium oxide abrasive ball 200 grams, ball milling is 1 hour on planetary ball mill, adds PVB 1 gram then; Continued ball milling 2 hours; Vacuumize then and handled 2～3 minutes, remove the air in the slurry, obtain the lanthanum strontium titanate doping and be coated with slurry.
Get strontium lanthanum manganese oxide (La
0.8Sr
0.2MnO
3) powder 20 grams, butanone 20 grams, ethanol 10 grams, triethanolamine 0.6 gram; Add 60 gram zirconium oxide abrasive balls, ball milling is 1 hour on planetary ball mill, adds PVB 0.6 gram then; Dibutyl phthalate 0.6 gram, polyethylene glycol 0.6 gram continued ball milling 2 hours; Vacuumize then and handled 2～3 minutes, remove the air in the slurry, obtain strontium lanthanum manganese oxide and be coated with slurry.
2, the preparation of the tubular type SOFC monocell of anode-supported
Dipping one deck electrolyte slurry (thickness is about 55 μ m) on the anode support tube biscuit, said electrolytical material is SSZ (Zr
0.89Sc
0.1Ce
0.01O
2), treat it and wipe the part electrolyte with cotton swab after dry that (area is about 2cm to make anode expose the rectangular zone of a slice
2), then with writing brush with La
0.4Sr
0.6TiO
3The slurry brushing is at this bar-shaped zone, and must be with the slurry brushing to covering whole strip region fully, otherwise anode and electrolytical edge be prone to cause leak gas, and this can reduce the open circuit voltage of battery.Treat the La on the pipe
0.4Sr
0.6TiO
3Behind the slurry drying, continue to brush La above that
0.8Sr
0.2MnO
3Slurry, and put into oven drying.Then tubular type SOFC biscuit being put into Muffle furnace calcines.Anode support tube, electrolyte and connector burnt 10 hours at 1300 ℃ altogether.
Ceramic connector and the part electrolyte area adjacent with ceramic connector are covered with adhesive tape fully; With the exposed compound dipping composite cathode of electrolyte area slurry; Wherein the composite cathode slurry is that 70: 30 strontium lanthanum manganese oxide of mass ratio is mixed with the stable zirconia of scandium, and the mixed solvent (mass ratio is 1: 2) that adds alcohol and butanone is processed slurry; After treating the cathode slurry drying, put into Muffle furnace and heat-treat, heat treated temperature is 1200 ℃, and the time is 5 hours; Obtain the tubular type SOFC monocell (anode-supported tubular type SOFC) of present embodiment.
Through detecting the tubular type SOFC monocell of present embodiment 5 gained, its anode-supported thickness of pipe wall is 0.6mm, and the dielectric substrate thickness is 40 μ m, and ceramic connector tunic is thick to be 40 μ m; The thickness of cathode layer is 30 μ m.
With H
2Can know that for fuel carries out performance test with the tubular type SOFC monocell of present embodiment gained according to the method for embodiment 2 its battery performance is along with the rising of temperature is significantly increased, and realize good power output.
Can know carrying out the test of series-connected cell pile power generating according to embodiment 4 with two tubular type SOFC of present embodiment; Under 800 ℃ and 850 ℃; The open circuit voltage of battery pile all more than 2V, equals two monocell open circuit voltage sums basically, explains that the battery series connection is successful.
The preparation of tubular type SOFC monocell may further comprise the steps:
1, the preparation of single-layer ceramic connector slurry:
At first, adopt liquid phase method to prepare the higher doping chromic acid lanthanum powder (La of sintering activity
0.7Ca
0.3Cr
0.9Zn
0.05O
3).Get doping chromic acid lanthanum powder 50g, add 60 gram butanone and 40 gram ethanol, add zirconium oxide abrasive ball 200 grams then as solvent; Ball milling is 1 hour on planetary ball mill; Add the PVB1.2 gram then, continued ball milling 2 hours, vacuumize then and handled 2～3 minutes; Remove the air in the slurry, the slurry that is coated with of the chromic acid lanthanum that obtains mixing.
2, the preparation of the tubular type SOFC monocell of anode-supported
Dipping one deck electrolyte slurry (the about 15 μ m of thickness) on the anode support tube biscuit, said electrolytical material is the zirconia that the 8%mol yttrium mixes, and treats it and wipes the part electrolyte with cotton swab after dry, (area is about 2cm to make anode expose the rectangular zone of a slice
2), then with writing brush with the slurry brushing of doping chromic acid lanthanum at this bar-shaped zone, and must be, otherwise anode and electrolytical edge be prone to cause leak gas with the slurry brushing to covering whole strip region fully, this can reduce the open circuit voltage of battery, puts into oven drying.Then tubular type SOFC biscuit being put into Muffle furnace calcines.Anode support tube, electrolyte and connector burnt 6 hours at 1350 ℃ altogether.
Through detecting the tubular type SOFC monocell of present embodiment 6 gained, its anode-supported thickness of pipe wall is 1mm, and the dielectric substrate thickness is 10 μ m, and ceramic connector tunic is thick to be 30 μ m; The thickness of cathode layer is 60 μ m.
With H
2Can know that for fuel carries out performance test with the tubular type SOFC monocell of present embodiment gained according to the method for embodiment 2 performance of its performance and embodiment 1 battery is suitable, battery performance is along with the rising of temperature is significantly increased, and realized good power output.But owing to adopt the doping chromic acid lanthanum powder limited amount of liquid phase method preparation, it remains in certain restriction in the large-scale commercial applications application facet.Then there are not the problems referred to above in the lanthanum strontium titanate doping of solid reaction process preparation and commercially available strontium lanthanum manganese oxide powder.
Can know carrying out the test of series-connected cell pile power generating according to embodiment 4 with two tubular type SOFC of present embodiment; Under 800 ℃ and 850 ℃; The open circuit voltage of battery pile all more than 2V, equals two monocell open circuit voltage sums basically, explains that the battery series connection is successful.
Embodiment 7
The preparation of tubular type SOFC monocell may further comprise the steps:
1, the preparation of double-layer ceramic connector slurry:
At first, adopt solid reaction process to prepare some lanthanum strontium titanate doping (La
0.4Sr
0.6TiO
3) powder.Strontium lanthanum manganese oxide (La
0.8Sr
0.2MnO
3) powder is the product of commercially available U.S. Fuel Cell Materials Corporation company.Get lanthanum strontium titanate doping powder 44 grams earlier, absolute ethyl alcohol 100 grams, triethanolamine 1.5 grams; Add zirconium oxide abrasive ball 200 grams, ball milling is 1 hour on planetary ball mill, adds PVB (Pioloform, polyvinyl acetal) 1 gram then; Continued ball milling 2 hours; Vacuumize then and handled 2～3 minutes, remove the air in the slurry, obtain the lanthanum strontium titanate doping and be coated with slurry.
Get strontium lanthanum manganese oxide (La
0.8Sr
0.2MnO
3) powder 20 grams, butanone 20 grams, ethanol 10 grams, triethanolamine 0.6 gram; Add 60 gram zirconium oxide abrasive balls, ball milling is 1 hour on planetary ball mill, adds PVB 0.6 gram then; Dibutyl phthalate 0.6 gram, polyethylene glycol 0.6 gram continued ball milling 2 hours; Vacuumize then and handled 2～3 minutes, remove the air in the slurry, obtain strontium lanthanum manganese oxide and be coated with slurry.
2, the preparation of the tubular type SOFC monocell of anode-supported
On the anode support tube biscuit, flood electrolyte slurry, said electrolytical material is scandium doped zirconia (SSZ:Zr
0.89Sc
0.1Ce
0.01O
2), treat it and wipe the part electrolyte with cotton swab after dry that (area is about 2cm to make anode expose the rectangular zone of a slice
2), then with writing brush with La
0.4Sr
0.6TiO
3The slurry brushing is at this bar-shaped zone, and must be with the slurry brushing to covering whole strip region fully, otherwise anode and electrolytical edge be prone to cause leak gas, and this can reduce the open circuit voltage of battery.Treat the La on the pipe
0.4Sr
0.6TiO
3Behind the slurry drying, continue to brush La above that
0.8Sr
0.2MnO
3Slurry, and put into oven drying.Then tubular type SOFC biscuit being put into Muffle furnace calcines.Anode support tube, electrolyte and connector burnt 3 hours at 1400 ℃ altogether.
Ceramic connector and the part electrolyte area adjacent with ceramic connector are covered with adhesive tape fully; With the exposed compound dipping composite cathode of electrolyte area slurry; Wherein the composite cathode slurry is that 70: 30 strontium lanthanum manganese oxide of mass ratio is mixed with the stable zirconia of scandium, and the mixed solvent (mass ratio is 1: 2) that adds alcohol and butanone is processed slurry; After treating the cathode slurry drying, put into Muffle furnace and heat-treat, heat treated temperature is 1200 ℃, and the time is 3 hours; Obtain the tubular type SOFC monocell (anode-supported tubular type SOFC) of embodiment 1.
Through detecting the tubular type SOFC monocell of present embodiment 1 gained, its anode-supported thickness of pipe wall is 1.2mm, and the dielectric substrate thickness is 15 μ m, and ceramic connector tunic is thick to be 60 μ m; The thickness of cathode layer is 60 μ m.
With H
2Can know that for fuel carries out performance test with the tubular type SOFC monocell of present embodiment gained according to the method for embodiment 2 performance of its performance and embodiment 1 battery is suitable, battery performance is along with the rising of temperature is significantly increased, and realized good power output.
Can know carrying out the test of series-connected cell pile power generating according to embodiment 4 with two tubular type SOFC of present embodiment; Under 800 ℃ and 850 ℃; The open circuit voltage of battery pile all more than 2V, equals two monocell open circuit voltage sums basically, explains that the battery series connection is successful.
Claims (10)
1. anode-supported tubular type SOFC; It is characterized in that; The anode support tube that comprises end sealing, the outer surface of said anode support tube are provided with strip pottery connector layer, and said strip pottery connector layer is parallel to the tubular axis of anode support tube; Blind end from the lateral surface of anode support tube extends to openend, and length is no longer than anode support tube; The part of not establishing ceramic connector layer on the said anode-supported tube outer surface is provided with dense electrolyte layer, and said dense electrolyte layer and strip pottery connector layer adjoin and cover fully the outer surface of anode support tube each other; Said anode support tube, dense electrolyte layer and ceramic connector layer burn altogether and are one; The dense electrolyte layer of said anode support tube lateral surface also is provided with cathode layer outward, and cathode layer does not link to each other with ceramic connector layer.
2. like claims 1 described anode-supported tubular type SOFC, it is characterized in that said anode-supported thickness of pipe wall is 0.6～1.2mm; Said dielectric substrate thickness is 10～40 μ m; Said ceramic connector tunic is thick to be 30～60 μ m; The thickness of said cathode layer is 30～60 μ m.
3. like claims 1 described anode-supported tubular type SOFC, it is characterized in that said anode support tube comprises passive supporting layer, said supporting layer also is coated with one or more layers electrochemical function layer outward.
4. like claims 1 described anode-supported tubular type SOFC; It is characterized in that said dielectric substrate is selected from a kind of in the stable zirconia layer of yttrium, scandium stable zirconia layer, gadolinium doping of cerium oxide layer, samarium doping of cerium oxide layer and the gallic acid strontium lanthanum layer or at least two kinds composite bed among them.
5. like claims 1 described anode-supported tubular type SOFC, it is characterized in that said ceramic connector layer is connector individual layer or connector composite bed.
6. like claims 1 described anode-supported tubular type SOFC, it is characterized in that, be provided with the interior pipe of logical fuel gas in the said anode support tube, filled and process nickel between the inwall of said interior pipe and anode support tube; The material of pipe is conductive metallic material or ceramic material in said.
7. like claims 6 described anode-supported tubular type SOFCs, it is characterized in that, also be provided with the catalyst of realizing fuel reforming on the inwall of said interior pipe.
8. like the arbitrary described anode-supported tubular type preparation of solid oxide fuel cell of claims 1-7, comprise the steps:
1) with outer surface dipping one deck electrolyte slurry of the anode support tube biscuit of end sealing, treat the dielectric substrate drying after, along anode support tube axially wipe the part electrolyte, make the outer surface of anode support tube biscuit expose a continuous rectangular zone;
2) one or more layers ceramic connector slurry of brushing on the stripe region of step 1) gained, treat ceramic connector slurry drying after, put into altogether burning of Muffle furnace, obtain being sintered to anode support, dielectric substrate and the connector layer of one;
3) ceramic connector and the part electrolyte area adjacent with ceramic connector are covered with adhesive tape fully; With the exposed compound impregnated cathode slurry of electrolyte area; After treating the cathode slurry drying, put into Muffle furnace and heat-treat, obtain said anode-supported tubular type SOFC.
9. preparation method as claimed in claim 8 is characterized in that step 2) in, said temperature of burning altogether is 1300～1400 ℃, temperature retention time is 3～10 hours; In the step 3), said composite cathode slurry is that strontium lanthanum manganese oxide and the stable zirconia of scandium form.
10. the battery pile of an anode-supported tubular type SOFC is for mixing arbitrary described anode-supported tubular type SOFC series connection of a plurality of claims 1-7 or connection in series-parallel.
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| CN103094595A (en) * | 2013-01-22 | 2013-05-08 | 中国科学院上海硅酸盐研究所 | Anode support tube type solid oxide fuel cell and assembling method thereof |
| CN103280592A (en) * | 2013-06-07 | 2013-09-04 | 苏州诺信创新能源有限公司 | Solid oxide fuel cell combination |
| CN103746128A (en) * | 2014-01-10 | 2014-04-23 | 上海交通大学 | Double-layer coating on metal connector surface of high-temperature solid oxide cell and preparation method thereof |
| CN104638287A (en) * | 2015-01-28 | 2015-05-20 | 潮州三环（集团）股份有限公司 | Method for preparing anode-supported type solid oxide fuel battery |
| CN106207221A (en) * | 2016-08-11 | 2016-12-07 | 山西大学 | A kind of method preparing tubular solid oxide fuel cell |
| CN106848358A (en) * | 2017-04-18 | 2017-06-13 | 中国科学技术大学 | A kind of doped cerium oxide base SOFC and preparation method thereof |
| CN107946604A (en) * | 2017-11-22 | 2018-04-20 | 江苏科技大学 | A kind of method that infusion process prepares segmentation series connection tubular solid oxide fuel cell |
| CN108054394A (en) * | 2017-12-07 | 2018-05-18 | 北京理工大学 | The synthetic method of solid oxide fuel cell strontium titanate base material |
| CN109755616A (en) * | 2017-11-08 | 2019-05-14 | 中国科学院宁波材料技术与工程研究所 | Hollow symmetrical structure twin cathode Solid-state fuel cell with interior Reforming performance and preparation method thereof |
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| CN113748547A (en) * | 2019-02-20 | 2021-12-03 | 艾瑞尔撒马利亚中心大学 | Solid oxide fuel cell with scandium-modified nickel felt anode current collector |
| CN113745617A (en) * | 2021-09-10 | 2021-12-03 | 广东石油化工学院 | Novel double-sheet integrated SOFC cell unit, manufacturing process and cell stack |
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