CN100589271C - Method for preparing hollow fiber-type solid-oxide fuel battery - Google Patents
Method for preparing hollow fiber-type solid-oxide fuel battery Download PDFInfo
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- CN100589271C CN100589271C CN200810024683A CN200810024683A CN100589271C CN 100589271 C CN100589271 C CN 100589271C CN 200810024683 A CN200810024683 A CN 200810024683A CN 200810024683 A CN200810024683 A CN 200810024683A CN 100589271 C CN100589271 C CN 100589271C
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a method for preparing a hollow fiber type solid oxide fuel cell, comprising the following steps of: adding anode material into an organic solvent containing organisms to mix evenly and produce an anode billet, evenly spraying organic solvent suspension containing electrolyte powder onto the thermally treated anode billet to produce an electrolyte layer; adding cathode powder and an organic pore-forming agent into an organic solvent to disperse evenly to produce an organism suspension containing the cathode powder and spraying the same onto the electrolyte layer uniformly to produce the hollow fiber type solid oxide fuel cell after thermal treatment. In the method, due to the adoption of the hollow fiber type SOFC structure, the diameter of a tube type SOFC is greatly reduced, the power density of the SOFC in unit area is increased by three to ten times. Meanwhile, the reduction of the diameter also greatly reduces the thicknesses of electrodes and electrolytes,and hence the resistance on the electrodes and the electrolytes is reduced correspondingly and the performance of the cell is improved. The method can cut the preparation cost and simplify the preparation technology.
Description
Technical field
The invention belongs to novel energy, materials processing and power domain, be specifically related to a kind of hollow fiber type preparation of solid oxide fuel cell.
Background technology
Solid Oxide Fuel Cell (SOFC) is a kind of device that chemical energy is converted into electric energy.It is made of the electrolyte of one deck densification and the electrode of two-layer porous, and entire cell all adopts solid material, and this makes the life-span of battery can reach 40000～80000 hours.Different with the generation mode of routine, need not participate in by large-size machine during the SOFC generating, therefore whole process is very quiet, does not need to use lubricating oil that motor is safeguarded simultaneously, has reduced the use cost of SOFC.The working temperature of SOFC higher (500～1000 ℃), this makes the generating efficiency of SOFC can reach 40%～50%, if waste heat is used for thermo-mechanical power generation, the comprehensive utilization ratio of energy can reach more than 80%.Hot operation also makes SOFC so not harsh aspect the selection of fuel, and hydrogen, carbon monoxide, alcohols (methyl alcohol, ethanol) and alkane (methane, propane even isooctane) can both be as its fuel.Wherein, most of fuel is the recyclability resource, and this advantage makes SOFC become particularly important in today of energy shortage.And the use of non-fossil class A fuel A has reduced the generation of sulfur-containing oxide and nitrogen-containing oxide, and the efficient utilization of adding fuel can reduce emission of carbon-dioxide, and this makes SOFC become a kind of Blast Furnace Top Gas Recovery Turbine Unit (TRT) of very clean environment firendly again.
In actual applications, the power of monomer SOFC is very limited, in order to obtain bigger power, need with several monocells in every way (series, parallel, series-parallel connection) be assembled into battery pile (Stack).The SOFC of extensive generating piles up the battery pile that forms by single cell units by various structures, uses two kinds of maximum structures at present and is: flat and tube designs.Compare with flat-plate-type solid-oxide fuel battery, tubular solid oxide fuel cells (TSOFC) is more suitable in building big capacity power station because of characteristics such as the Sealing Technology of high mechanical properties, high thermal shock resistance, simplification, the integrated performances of high modularization.Because to prepare difficulty bigger for tubular cells, family surplus the unit that is engaged in the TSOFC research and development has only 30, and realize the above generate output of 100kW have only Siemens-Xi room power (SWPC) company.In addition, Acumentrics company and fuel cell technology company (Fuel Cell Technology FCT) has also obtained great advance in the exploitation of small-sized TSOFC.
But traditional tubular type SOFC generally needs the thicker supporter of one deck to guarantee the enough mechanical strengths of SOFC because the pipe diameter is bigger, generally adopts male or female support type SOFC, and this increases the resistance on the male or female, and the generating capacity of battery descends.And the response area that provides in traditional tubular type SOFC unit volume is still limited, so volumetric power density is still waiting to improve.
Summary of the invention
The object of the present invention is to provide a kind of high volumetric power density and be convenient to New type of S OFC configuration of production application and preparation method thereof.
Purpose of the present invention can reach by following measure:
A kind of hollow fiber type preparation of solid oxide fuel cell comprises the steps:
(1) anode material is added contain and mixes aftershaping in the organic organic solvent and make the anode base substrate, behind the dry solidification at 800～1200 ℃ of following heat treatment 3～96h;
(2) organic solvent suspension that will contain the electrolyte powder evenly sprays on the heat treated anode base substrate, heating anode base substrate to temperature is 80～250 ℃ during spraying, to spray electrolytical anode base substrate at 1200～1600 ℃ of following heat treatment 3～96h, make dielectric substrate;
(3) make the organic substance suspension that contains cathode powder with being uniformly dispersed in cathode powder and the organic pore-forming agents adding organic solvent, and evenly spray on the dielectric substrate, heating anode base substrate to temperature is 80～250 ℃ during spraying, spray the back at 800～1200 ℃ of following heat treatment 3～96h, made the hollow fiber type Solid Oxide Fuel Cell.
Wherein anode material is selected from one or more in transition metal oxide, lanthanide metal oxide or the perofskite type oxide, can also comprise that perhaps mass content is 10～60% electrolyte.Anode material can also comprise that mass content is 0.1～30% noble metal.
Wherein organic substance is polyvinyl alcohol, cellulose acetate, starch, polyvinyl butyral resin, polysulfones, polyether sulfone or polyester.Organic solvent is selected from methyl alcohol, ethanol, ethylene glycol, isopropyl alcohol, acetone, toluene, N, N-dimethyl acetyl ammonia or N, one or more in the N-dimethyl sulfoxide (DMSO).
Wherein cathode powder is selected from one or more in perofskite type oxide or the noble metal, as La
0.6Sr
0.4MnO
3(LSM64), La
0.6Sr
0.4FeO
3(LSF64), Ba
0.5Sr
0.5Co
0.8Fe
0.2O
3(BSCF), La
0.6Sr
0.4Co
0.2Fe
0.8O
3, La
0.8Sr
0.2MnO
3(LSM82), La
0.8Sr
0.2Sc
0.2Mn
0.8O
3(LSCM)), La
2NiO
4, PrBaCo
2O
5, Pt or Pd etc., perhaps above-mentioned substance and electrolytical combination.
Wherein electrolyte is the stable zirconia (as: Y of yttrium
0.18Zr
0.82O
1.91(YSZ)), the stable zirconia (as: Sc of scandium
0.2Zr
0.80O
1.9(ScSZ)), samarium doping of cerium oxide (as: Sm
0.10Ce
0.9O
1.95(SDC), Gd
0.20Ce
0.8O
1.9Or lanthanum gallium based perovskite type (as: La (GDC))
0.8Sr
0.2Ga
0.8Mg
0.2O
3(LSGM)) oxide electrolyte.Organic pore-forming agents is starch, glycerine, polyvinyl alcohol, ethyl cellulose or polyvinyl butyral resin.
Purpose of the present invention specifically can reach by following measure:
A kind of hollow fiber type SOFC, its concrete preparation process is:
(1) preparation of anode support
At first, organic substance is dissolved in the organic solvent in 20～120 ℃, makes organic solution after dissolving stirs;
The percentage by weight of described component is: organic substance: organic solvent=5～40%: 60～90%;
Described organic substance is preferably selected for use from polyvinyl alcohol, cellulose acetate, starch, polyvinyl butyral resin, polysulfones, polyether sulfone or polyester etc.;
Described solvent is preferably selected from methyl alcohol, ethanol, ethylene glycol, acetone, toluene, N, N-dimethyl acetyl ammonia or N, one or more in the N-dimethyl sulfoxide (DMSO);
Then, anode material is added in the above-mentioned organic solution, under 20～50 ℃, mix by ball milling;
Described anode material is: transition metal oxide (as: NiO, CuO, Fe
2O
3Deng), lanthanide metal oxide (as: La
2O
3, Sm
2O
3Deng) or perofskite type oxide (as: lanthanum manganate that chromium mixes, the lanthanum manganate that iron mixes, the lanthanum manganate that scandium mixes etc.); Described anode material can also be the mixture of above-mentioned substance and electrolyte (as: zirconia (YSZ) that yttrium is stable, the zirconia (ScSZ) that scandium is stable, samarium doping of cerium oxide (SDC), lanthanum gallium based perovskite type oxide (LSGM) electrolyte etc.); Mass ratio is an anode material: electrolyte=40～90%: 10～60%.
Described anode material can also add the composite material that noble metal (as Ag, Pt, Pd, Ru etc.) is formed for above-mentioned anode; The quality of noble metal accounts for 0.1～30% of anode.
Anode material and organic mass ratio are: 60～99%: 1～40%.
Then, with the above-mentioned organic solution that contains anode material, through passing through the extrusion molding of system film die after the vacuum degassing, make base substrate, dry solidification under room temperature or vacuum state promptly gets the anode base substrate; Again with the anode base substrate at 800～1200 ℃ of following heat treatment 3～96h;
Described system film die is special copper, the doughnut spinning head apparatus of aluminum or stainless steel;
The internal diameter of described anode base substrate is 0.4～2mm, and wall thickness is 0.2～0.8mm, and length is 5～150cm.
(2) electrolytical preparation
Dielectric substrate is by wet granular spray-on process (Wet Powder Spraying, WPS) preparation.The organic solvent suspension that will contain the electrolyte powder is passed through sprayer unit, be sprayed onto uniformly on the above-mentioned heat treated anode support, need heat the anode base substrate during spraying, temperature is 80～250 ℃, carrier gas can be any nonhazardous gas, carrier gas flux is 20～100mL/min, and gas pressure is 1～5atm, spray time 1～10s.The electrolyte of the anode-supported that above-mentioned spraying is finished places high-temperature electric resistance furnace to heat-treat, and makes the electrolyte densification, and sintering temperature is 1200～1600 ℃, and heating rate is 0.5～20 ℃/min, temperature retention time 3～96h.
The electrolyte powder adopts hydro thermal method synthetic, and the electrolyte particle diameter is 50～400nm;
The electrolyte powder is placed organic solvent, mix 30～240min by high-energy ball milling machinery and make it even;
Organic solvent is preferably selected for use in ethylene glycol, isopropyl alcohol, acetone, ethanol or methyl alcohol etc.;
The mass ratio of electrolyte powder and organic solvent is 0.5～30: 100;
(3) preparation of negative electrode
Cathode powder and organic pore-forming agents added in the organic solvent to be uniformly dispersed through high-energy ball milling make the organic substance suspension that contains cathode powder, utilize the above-mentioned spraying method identical that negative electrode suspension is sprayed onto fine and close bath surface with electrolyte, need heat the anode base substrate during spraying, temperature is 80～250 ℃, heat treatment makes required battery in electric furnace again, sintering temperature is 800～1200 ℃, and heating rate is 0.5～20 ℃/min, temperature retention time 3～96h.Final battery interior diameter only is 0.3～1.5mm, wall thickness 0.15～0.60mm, length be 3～120cm (after high-temperature heat treatment, sintering can take place in ceramic material, shrinkage about 30% or more than, so size is inconsistent before and after can causing sintering).
Cathode material is the various perofskite type oxides (as: lanthanum manganate (as: La of strontium doping
0.8Sr
0.2MnO
3(LSM82)), the lanthanum manganate (as: La of strontium scandium doping
0.8Sr
0.2Sc
0.2Mn
0.8O
3(LSCM)), noble metal (as: Pt, Pd etc.) or other perovskite-like type oxide (as: La
2NiO
4, PrBaCo
2O
5Deng); Cathode material also can be the mixture that above two or more material is formed arbitrarily, with and the mixture (as: Ba that forms arbitrarily with electrolyte
0.5Sr
0.5Co
0.8Fe
0.2O
3(BSCF)+and Ag, LSM+YSZ, LSCM+ScSZ+Pd, BSCF+SDC+Ag etc.).
Organic pore-forming agents is preferably selected for use in starch, glycerine, polyvinyl alcohol, polyvinyl butyral resin, ethyl cellulose or various material with carbon elements etc.; Organic solvent is preferably selected for use in ethylene glycol, isopropyl alcohol, acetone, ethanol or methyl alcohol etc.; The mass ratio of organic pore-forming agents and organic solvent is 5～30: 60～120, and the mass ratio of cathode material and organic solvent is 5～20: 90～120.
The thickness of the negative electrode after the heat treatment is 5～200 μ m.
Beneficial effect of the present invention:
The present invention adopts hollow fiber type SOFC structure, has dwindled the diameter of tubular type SOFC greatly, makes the power density of SOFC in unit volume improve 3～10 times.Dwindling of diameter also makes electrode and electrolytical thickness significantly reduce simultaneously, so the resistance on electrode and the electrolyte descends the raising battery performance thereupon.In addition, the present invention adopts the WPS technology to prepare the preparation cost that electrolyte and negative electrode can reduce SOFC, simplifies the preparation technology of SOFC.
Description of drawings
Fig. 1 is scanning electron microscopy (SEM) photo of bath surface behind the embodiment of the invention one sintering.
Fig. 2 is a negative electrode behind the embodiment of the invention one sintering | electrolyte | and the SEM photo in anode trilamellar membrane cross section.
Fig. 3 is current density-voltage (I-V) and current density-power density (I-W) curve of the embodiment of the invention one hollow fiber type SOFC.
Fig. 4 is a negative electrode behind the embodiment of the invention two sintering | electrolyte | and the SEM photo in anode trilamellar membrane cross section.
Fig. 5 is I-V and the I-W curve of the embodiment of the invention two hollow fiber type SOFC.
Embodiment
Embodiment 1:Ni+Y
0.18Zr
0.82O
1.91(YSZ) | YSZ|La
0.6Sr
0.4MnO
3(LSM64) preparation of hollow fiber type SOFC and performance test
At first, with the 5g polyvinyl butyral resin, 40g ethanol, 10g acetone, 10g N, the premixed of N-dimethyl acetyl ammonia takes by weighing 40gNiO and 60gYSZ powder more respectively and adds in the stainless steel jar mill, forms organic substance-metal oxide paste behind the ball milling 24h.To make the anode base substrate some with extruding by the system film die after the above-mentioned slurry vacuum degassing, with this base substrate under the vacuum state in 80 ℃ of dry 24h be placed in the electric furnace 1000 ℃ of heat treatment 5h (heating rate be 5 ℃/after min) dry body body (internal diameter 1.5mm, thickness 0.8mm, long 200mm).
Then, with electrolyte powder 10g YSZ, 20g ethylene glycol, the 80g isopropyl alcohol adds in the ball grinder, and ball milling 2h makes electrolyte slurry under the 500rpm rotating speed.By the excusing from death sprayer inferior electrolyte slurry is sprayed on the above-mentioned anode dry body body, anode dry body body must be placed on the heating station in spraying process, and temperature is 200 ℃, and carrier gas is an argon gas, and flow is 50mL/min, and gas pressure is 1.2atm, spray time 4s.The double-deck base substrate of the electrolyte of the anode-supported that above-mentioned spraying is finished places high-temperature electric resistance furnace heat treatment, and treatment temperature is 1400 ℃, and heating rate is 3 ℃/min, temperature retention time 5h.After finishing, heat treatment obtains the electrolyte duplicature of anode-supported.Fig. 1 can see from photo that for electrolytical scanning electron microscopy (SEM) photo after the heat treatment whole bath surface is fine and close fully, exists without any hole or crack.
Secondly, by high-energy ball milling with 5g LSM64,10g ethylene glycol, 40g isopropyl alcohol and 5g polyvinyl alcohol (organic pore-forming agents) add in the ball grinder, ball milling 2h makes cathode slurry under the 500rpm rotating speed.The secondary cathode slurry is sprayed on the dielectric substrate of electrolyte duplicature of above-mentioned anode-supported by the excusing from death sprayer, anode dry body body must be placed on the heating station in spraying process, and temperature is 200 ℃, carrier gas is an argon gas, flow is 50mL/min, and gas pressure is 1.2atm, spray time 6s.The negative electrode that spraying is good | electrolyte | the anode trilamellar membrane places high-temperature electric resistance furnace heat treatment, and treatment temperature is 1050 ℃, and heating rate is 5 ℃/min, temperature retention time 5h.Get hollow fiber type SOFC after the heat treatment.Fig. 2 is a negative electrode | electrolyte | and the SEM photo in anode trilamellar membrane cross section, electrolyte are approximately 10 μ m, almost do not have the hole, and density is very high, so ionic conducting property is good.The negative electrode anode is loose structure, and they are connected very closely with electrolytical, help the conduction of oxonium ion in negative electrode-electrolyte or electrolyte-anodic interface.
At last, carry out the test of hollow fiber type fuel battery performance.Interior pipe feeds hydrogen and acts as a fuel, and the outer tube bubbling air is as oxidant.As can be seen from Figure 3, open circuit voltage is that 1.03V this and theoretical value are very approaching in the time of 850 ℃, illustrates that there is not flaw in electrolyte, and power density can reach 917mW/cm
2
Embodiment 2:Ni+Sc
0.2Zr
0.80O
1.9(ScSZ) | ScSZ|La
0.6Sr
0.4FeO
3(LSF64) preparation of hollow fiber type SOFC and performance test
At first, with the 5g polyvinyl butyral resin, 40g ethylene glycol, the 10g butanone, 20g N, the premixed of N-dimethyl sulfoxide (DMSO) takes by weighing 40gNiO and 60g ScSZ powder more respectively and adds in the stainless steel jar mill, forms organic substance-metal oxide paste behind the ball milling 48h.Some with going out to make the anode base substrate by system film die skill after the above-mentioned slurry vacuum degassing, with this base substrate under the vacuum state in 100 ℃ of dry 24h be placed in the electric furnace 1000 ℃ of heat treatment 5h (heating rate be 5 ℃/after min) dry body body (internal diameter 1mm, thickness 0.6mm, long 150mm).
Then, with electrolyte powder 10g ScSZ, 10g ethylene glycol, 10g toluene, the 80g isopropyl alcohol adds in the ball grinder, and ball milling 2h makes electrolyte slurry under the 500rpm rotating speed.By the excusing from death sprayer inferior electrolyte slurry is sprayed on the above-mentioned anode dry body body, anode dry body body must be placed on the heating station in spraying process, and temperature is 200 ℃, and carrier gas is an argon gas, and flow is 50mL/min, and gas pressure is 1.5atm, spray time 8s.The double-deck base substrate of the electrolyte of the anode-supported that above-mentioned spraying is finished places high-temperature electric resistance furnace heat treatment, and treatment temperature is 1400 ℃, and heating rate is 4 ℃/min, temperature retention time 5h.After finishing, heat treatment obtains the electrolyte duplicature of anode-supported.
Secondly, by high-energy ball milling with 5g LSF64,10g ethylene glycol, 40g isopropyl alcohol and 10g starch (organic pore-forming agents) add in the ball grinder, ball milling 2h makes cathode slurry under the 500rpm rotating speed.The secondary cathode slurry is sprayed on the dielectric substrate of electrolyte duplicature of above-mentioned anode-supported by the excusing from death sprayer, anode dry body body must be placed on the heating station in spraying process, and temperature is 250 ℃, carrier gas is a nitrogen, flow is 30mL/min, and gas pressure is 1.0atm, spray time 10s.The negative electrode that spraying is good | electrolyte | the anode trilamellar membrane places high-temperature electric resistance furnace heat treatment, and treatment temperature is 1000 ℃, and heating rate is 5 ℃/min, temperature retention time 3h.Get hollow fiber type SOFC after the heat treatment.Fig. 4 is a negative electrode | electrolyte | and the SEM photo in anode trilamellar membrane cross section, electrolyte are approximately 16 μ m, almost do not have the hole, and density is very high, so ionic conducting property is good.The negative electrode anode is loose structure, and they are connected very closely with electrolytical, help the conduction of oxonium ion in negative electrode-electrolyte or electrolyte-anodic interface.
At last, carry out the test of hollow fiber type fuel battery performance.Interior pipe feeds hydrogen and acts as a fuel, and the outer tube bubbling air is as oxidant.As can be seen from Figure 5, open circuit voltage is that 1.06V this and theoretical value are very approaching in the time of 850 ℃, illustrates that there is not flaw in electrolyte, and power density can reach 600mW/cm
2
Embodiment 3:Ni+Sm
0.2Ce
0.8O
1.9(SDC) | preparation and the performance test of SDC|BSCF+SDC hollow fiber type SOFC
At first, with the 5g polyvinyl butyral resin, 40g ethylene glycol, the 10g butanone, 20g N, the premixed of N-dimethyl sulfoxide (DMSO) takes by weighing 40gNiO and 60g SDC powder more respectively and adds in the stainless steel jar mill, forms organic substance-metal oxide paste behind the ball milling 48h.Some with going out to make the anode base substrate by system film die skill after the above-mentioned slurry vacuum degassing, with this base substrate under the vacuum state in 100 ℃ of dry 24h be placed in the electric furnace 1000 ℃ of heat treatment 5h (heating rate be 5 ℃/after min) dry body body (internal diameter 1mm, thickness 0.6mm, long 150mm).
Then, with electrolyte powder 10g ScSZ, 10g ethylene glycol, 10g toluene, the 80g isopropyl alcohol adds in the ball grinder, and ball milling 2h makes electrolyte slurry under the 500rpm rotating speed.By the excusing from death sprayer inferior electrolyte slurry is sprayed on the above-mentioned anode dry body body, anode dry body body must be placed on the heating station in spraying process, and temperature is 200 ℃, and carrier gas is a nitrogen, and flow is 50mL/min, and gas pressure is 1.5atm, spray time 6s.The double-deck base substrate of the electrolyte of the anode-supported that above-mentioned spraying is finished places high-temperature electric resistance furnace heat treatment, and treatment temperature is 1400 ℃, and heating rate is 4 ℃/min, temperature retention time 5h.After finishing, heat treatment obtains the electrolyte duplicature of anode-supported.
Secondly, by high-energy ball milling with 1.5g BSCF, 3.5gSDC, 10g ethylene glycol, 40g isopropyl alcohol and 8g ethyl cellulose (organic pore-forming agents) add in the ball grinder, ball milling 4h makes cathode slurry under the 450rpm rotating speed.The secondary cathode slurry is sprayed on the dielectric substrate of electrolyte duplicature of above-mentioned anode-supported by the excusing from death sprayer, anode dry body body must be placed on the heating station in spraying process, and temperature is 250 ℃, carrier gas is a nitrogen, flow is 30mL/min, and gas pressure is 1.0atm, spray time 6s.The negative electrode that spraying is good | electrolyte | the anode trilamellar membrane places high-temperature electric resistance furnace heat treatment, and treatment temperature is 950 ℃, and heating rate is 10 ℃/min, temperature retention time 10h.Get hollow fiber type SOFC after the heat treatment.
Embodiment 4: organic matter removal replaces with cellulose acetate, and electrolyte replaces with La
0.8Sr
0.2Ga
0.8Mg
0.2O
3, anode material replaces with CuO, and negative electrode replaces with Ba
0.5Sr
0.5Co
0.8Fe
0.2O
3(BSCF)+Ag outside, other are with embodiment 1.
Embodiment 5: remove anode and replace with Cu+GDC+Sm
2O
3, negative electrode replaces with La
0.6Sr
0.4Co
0.2Fe
0.8O
3Outward, other are with embodiment 2.
Embodiment 6: remove anode and replace with Cu+La
0.8Sr
0.2Ga
0.8Mg
0.2O
3+ Pt, negative electrode replaces with La
0.6Sr
0.4Co
0.2Fe
0.8O
3Outside+the SDC+Ag, other are with embodiment 3.
Claims (10)
1, a kind of hollow fiber type preparation of solid oxide fuel cell is characterized in that comprising the steps:
(1) anode material is added contain and mixes aftershaping in the organic organic solvent and make the anode base substrate, behind the dry solidification at 800～1200 ℃ of following heat treatment 3～96h;
(2) organic solvent suspension that will contain the electrolyte powder evenly sprays on the heat treated anode base substrate, heating anode base substrate to temperature is 80～250 ℃ during spraying, to spray electrolytical anode base substrate at 1200～1600 ℃ of following heat treatment 3～96h, make dielectric substrate;
(3) make the organic substance suspension that contains cathode powder with being uniformly dispersed in cathode powder and the organic pore-forming agents adding organic solvent, and evenly spray on the dielectric substrate, heating anode base substrate to temperature is 80～250 ℃ during spraying, spray the back at 800～1200 ℃ of following heat treatment 3～96h, made the hollow fiber type Solid Oxide Fuel Cell.
2, preparation method according to claim 1 is characterized in that described anode material is selected from one or more in transition metal oxide or the lanthanide metal oxide, comprises also that perhaps mass content is 10～60% electrolyte.
3, preparation method according to claim 1 is characterized in that described anode material comprises that also mass content is 0.1～30% noble metal.
4, preparation method according to claim 1, the internal diameter that it is characterized in that described anode base substrate is 0.4～2mm, and wall thickness is 0.2～0.8mm, and length is 5～150cm.
5, preparation method according to claim 1 is characterized in that the organic substance described in the step (1) is polyvinyl alcohol, cellulose acetate, starch, polyvinyl butyral resin, polysulfones, polyether sulfone or polyester.
6, preparation method according to claim 1 is characterized in that described organic solvent is selected from methyl alcohol, ethanol, ethylene glycol, isopropyl alcohol, acetone, butanone, toluene, N, N-dimethyl acetyl ammonia or N, one or more in the N-dimethyl sulfoxide (DMSO).
7, preparation method according to claim 1 is characterized in that described cathode powder is selected from one or more in perofskite type oxide or the noble metal, perhaps above-mentioned substance and electrolytical combination.
8 according to claim 1,3 or 7 described preparation methods, it is characterized in that described electrolyte is the stable zirconia of the stable zirconia of yttrium, scandium, samarium doping of cerium oxide or lanthanum gallium based perovskite type oxide electrolyte.
9 preparation methods according to claim 1 is characterized in that described organic pore-forming agents is starch, glycerine, polyvinyl alcohol, ethyl cellulose or polyvinyl butyral resin.
10, preparation method according to claim 1, the interior diameter that it is characterized in that described hollow fiber type Solid Oxide Fuel Cell is 0.3～1.5mm, wall thickness 0.15～0.60mm, length is 3～120cm.
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| CN101752585B (en) * | 2010-01-21 | 2011-11-16 | 南京工业大学 | Solid oxide fuel battery system and preparation method thereof |
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| CN102347495B (en) * | 2011-10-19 | 2014-01-08 | 华北电力大学 | Solid oxide fuel cell structure and preparation method thereof |
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| CN104577142B (en) * | 2014-12-18 | 2017-07-07 | 天津工业大学 | A kind of preparation method of SOFC gradient-structure cathodic coating |
| 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 |
| CN106601986A (en) * | 2016-12-29 | 2017-04-26 | 中国电子科技集团公司第十八研究所 | Preparation method of AGO electrode |
| CN108039506B (en) * | 2017-12-07 | 2020-05-19 | 山东理工大学 | Preparation method of hollow fiber solid oxide fuel cell with petal-shaped cross section |
| CN111244467B (en) * | 2018-11-27 | 2021-08-03 | 中国科学院大连化学物理研究所 | Method for stabilizing cathode of solid oxide fuel cell |
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