CN109904497A - A kind of anti-carbon metal-supported solid oxide fuel cell and preparation method thereof - Google Patents
A kind of anti-carbon metal-supported solid oxide fuel cell and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to solid oxide fuel cell technical fields, and disclose a kind of anti-carbon metal-supported solid oxide fuel cell and preparation method thereof.The battery includes that the porous catalytic successively combined closely reforms layer, porous metals supporting layer, porous anode functional layer, dense electrolyte layer and porous cathode layer, wherein it includes Ni-M alloy and storage oxygen-water suction oxide that the porous catalytic, which reforms layer,；The porous metals supporting layer includes Ni-M alloy and MgO；The porous anode functional layer includes Ni-M alloy and fluorite structure oxide or Ni-M alloy and (ionic conduction type) perovskite structure oxide.The invention also discloses the preparation methods of respective battery.Fuel cell of the present invention when using hydrocarbon as fuel, can the long-term stable operation in hydrocarbon fuels, preparation process is low in cost, is suitable for large area monocell and large-scale production and manufactures, is with a wide range of applications.
Description
Technical field
The invention belongs to solid oxide fuel cell technical fields, support more particularly, to a kind of anti-carbon metal
Solid oxide fuel cell and preparation method thereof.
Background technique
Solid oxide fuel cell (SOFC) is a kind of by fossil fuel (coal, petroleum, natural gas and other hydrocarbonization
Close object) in chemical energy be converted directly into the electrochemical appliance of electric energy.SOFC have it is efficient, environmentally friendly, mute, can modularization etc. it is excellent
Point has a wide range of applications in stationary electric power plant, mobile traffic transport field and military field etc., successful application for
Alleviating energy crisis meets the needs of mankind are to amount of energy and quality and the living environment of the protection mankind etc. all with great
Meaning.
The structure type of traditional SOFC monocell generally includes electrolyte-supporting type (ES-SOFC), cathode support type (CS-
) and anode support type (AS-SOFC) SOFC.In said structure, provide mechanical support is usually ceramics or cermet material
Material, although its anti-corrosion property at high temperature is preferable, when encountering stress, shock and vibration and rapid thermal cycles, is easy to happen knot
Structure failure.With the development of low temperature in SOFC, cheap stainless steel material has been able in SOFC pile as connector
Using similarly, metal material is also used as the supporter of SOFC.Metallic support type SOFC (MS-SOFC) is referred to as third
For SOFC technology, compared with electrolyte-supporting type and electrode-supported SOFC, MS-SOFC is in cost, manufacture, mechanical strength and resistance to
Long property etc. have a significant advantage that (1) using lower-cost metal material as supporter, substantially reduce SOFC at
This；(2) mechanical strength that can effectively improve SOFC makes monocell and pile bear stronger shock and vibration or mechanical load；
(3) raising of monocell intensity is additionally beneficial to improve its machinability, can bear violent or quick operation and processing；(4)
MS-SOFC has better redox and thermal cycle, and good thermal cycle can realize the rapid starting/stopping of SOFC.
MS-SOFC is reported for the first time from the sixties in last century, until the mid-90 causes concern again, experienced again so far
Nearly research and development in 20 years.MS-SOFC technology is increasingly progressive, and especially with the development of low temperature in SOFC, advantage is more
One of add protrusion, and be increasingly becoming SOFC area research hot spot.In recent years, for the metal oxidation in the presence of MS-SOFC, member
The problems such as element diffusion, electrode poison and monocell prepares, has numerous research institutions in the world and is made that many work.But
It is mainly also to be only limitted to H about the research of MS-SOFC at present2For fuel stage, using hydrocarbon as fuel MS-SOFC
Research it is actually rare.It is directly the fuel of SOFC with hydrocarbon, can reduces because reforming bring system outside fuel
The production cost of complexity and valuableness, while fuel existing technical difficulty in terms of storage and transport can also be avoided, favorably
In the commercialization of SOFC technology, this is the hot spot and main direction of current SOFC technical research.
It the use of hydrocarbon is anode carbon distribution problem caused by fuel is MS-SOFC however, as other SOFC
The crucial problem urgently to be resolved faced.On the one hand, the deposition of carbon can hinder the diffusion of fuel gas inside the anode, reduce sun
The active reaction area of pole functional layer makes anode performance decaying until entirely ineffective；On the other hand, carbon distribution also results in metal branch
Dusting occurs for support body, destroys single-cell structure.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of anti-carbon metal-supported solid oxygen
Compound fuel cell and preparation method thereof, its object is to solve metallic support type solid oxide fuel cell with hydrocarbonization
The problem of being easy to produce carbon distribution when object is fuel is closed, allows metallic support type solid oxide fuel cell in hydrocarbon
Long-term stable operation in fuel.
To achieve the goals above, according to one aspect of the present invention, a kind of anti-carbon metal-supported solid oxidation is provided
Object fuel cell, which is characterized in that the porous catalytic including successively combining closely reforms layer, porous metals supporting layer, porous sun
Pole functional layer, dense electrolyte layer and porous cathode layer, wherein
It includes Ni-M alloy and storage oxygen-water suction oxide that the porous catalytic, which reforms layer,；
The porous metals supporting layer includes Ni-M alloy and MgO；
The porous anode functional layer includes Ni-M alloy and fluorite structure oxide or Ni-M alloy and ionic conduction
Type perovskite structure oxide；
Wherein the M element is one or more of Fe, Co, Cu, Sn.
Further, the storage oxygen-water suction oxide is alkaline earth or rear-earth-doped CeO2Base, BaCeO3Base, BaZrO3
Base, La2Ce2O7One or more of oxides such as base.
Further, the quality of the MgO is the 0.05-0.1% of the porous metals supporting layer quality；
Preferably, the porous catalytic reform layer with a thickness of 20 μm -40 μm, porosity 40%-60%；
Preferably, the porous metals supporting layer with a thickness of 500 μm -1000 μm, porosity 40%-60%；
Preferably, the porous anode functional layer with a thickness of 10 μm -20 μm, porosity 40%-60%；
Preferably, the dense electrolyte layer with a thickness of 10 μm -20 μm；
Preferably, the porous cathode layer with a thickness of 5 μm -20 μm, porosity 40%-60%.
Other side according to the invention provides a kind of preparation of anti-carbon metal-supported solid oxide fuel cell
Method, comprising the following steps:
S1 dehydrated alcohol is uniformly mixed with dimethylbenzene, and dispersing agent is added as solvent, the first presoma, pore creating material are formed
Mixed powder ball milling after the solvent is added, sequentially add plasticizer, first binder and defrother ball milling again, form curtain coating
Slurry, the tape casting after de-bubble, be supported voxel base layer after dry；
S2 is by the second presoma and fluorite structure oxide or the second presoma and ionic conduction type perovskite structure oxygen
Compound is uniformly mixed, and the second binder is added, the slurry of anode functional layer is obtained after grinding, by the slurry of the anode functional layer
It is printed on the supporter biscuit and anode functional layer thick film biscuit layer is made；
The second binder is added in electrolyte oxide powder by S3, the slurry of electrolyte layer is obtained after grinding, by the electricity
The slurry of solution matter layer, which is printed on anode functional layer thick film biscuit layer, is made electrolyte layer thick film biscuit layer；
S4 will above-mentioned manufactured successively close contact supporter biscuit layer, anode functional layer thick film biscuit layer and electrolyte layer
Thick film biscuit layer degreasing, sintering in air atmosphere, are then cooled to room temperature, obtain the half-cell of metal oxide support；
S5 mixes electron conductive type perovskite structure oxide and electrolyte powder, the second binder is added, after grinding
The slurry of cathode functional is obtained, the slurry of the cathode functional is printed onto the electrolyte layer side of the half-cell, is done
It is sintered and cooled room temperature after dry, the monocell of metal oxide support can be obtained；
Third presoma and storage oxygen-water suction oxide powder are uniformly mixed by S6, and the second binder is added, obtains after grinding
Catalysis is made in the support body layer side that the slurry of the catalytic reforming layer is printed onto the monocell by the slurry of catalytic reforming layer
Reform layer.
Further, first presoma is NiO, MgO and MOx, second presoma is NiO and MOx, described
Three presomas are NiO and MOx, wherein the M element is one or more of Fe, Co, Cu, Sn.
Further, in step S1, the first binder is polyvinyl butyral；
The quality of the MgO powder is the 0.05%-0.1% of the first forerunner weight.
Further, in step S2, second binder is the terpineol solution of ethyl cellulose, wherein the second
The mass fraction of base cellulose is 3.5%-4.5%,
In the slurry of the anode functional layer, the content of second binder is 30wt.%-40wt.%,
The mass ratio of the fluorite or ionic conduction type perovskite structure oxide and the second presoma is 3:7-4:6.
Further, in step S3, in the slurry of the electrolyte layer, the content of second binder is 30wt.%-
40wt.%.
Further, in step S4, the time of the degreasing is 4h-6h, and the temperature of the sintering is 1400 DEG C -1500
DEG C, the sintering heating and the rate to cool are 0.5 DEG C/min-5 DEG C/min；
In step S5,900 DEG C -1100 DEG C of the temperature of the sintering, the sintering heating and the rate to cool are 3
DEG C/min-5 DEG C/min, in the slurry of the cathode functional, the content of second binder is 40wt.%-60wt.%.
Further, in step S6,
In the slurry of the catalytic reforming layer, the content of second binder is 40wt.%-60wt.%,
The mass ratio of the storage oxygen-water suction oxide and the third presoma is 1:9-3:7.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, mainly have below
Technological merit:
(1) anti-carbon metal-supported solid oxide fuel cell of the invention effectively solves metal-supported solid oxide
The problem of fuel cell is easy to produce carbon distribution when using hydrocarbon as fuel, makes metal-supported solid oxide fuel cell
Can the long-term stable operation in hydrocarbon fuels, preparation process is low in cost, be suitable for large area monocell and rule
Modelling is manufactured, and is with a wide range of applications.
(2) MgO is added in porous metals supporting layer in the present invention, after can effectively inhibiting supporting layer to restore between metallic particles
Sintering shrinkage, structural stability of enhancing monocell when restoring in situ, and when monocell is through heat cycles, porous branch
Supportting layer has better dimensional stability；
(3) present invention reforms in porous catalytic and storage oxygen-water suction oxide is added in layer, can effectively improve catalytic reforming layer
Anti-carbon performance, meanwhile, hydrocarbon fuels through porous catalytic reform layer reform after, reach porous metals supporting layer and
The fuel element of porous anode functional layer changes, and generates carbon distribution so as to avoid supporter and anode；
(3) porous catalytic of the present invention reforms layer and is not necessarily to independent sintering step during the preparation process, in monocell operation
In-situ reducing can occur and be sintered, facilitate the interfacial contact for enhancing current collecting material and anode-side, improve afflux performance；
(4) monocell preparation process of the present invention is low in cost, is suitable for large area monocell and large-scale production system
It makes, and uses metal oxide for presoma, in air sinter molding, avoid inert atmosphere or reducing atmosphere uses,
Manufacturing cost is reduced, is with a wide range of applications.
Detailed description of the invention
Fig. 1 is anti-carbon metal-supported solid oxide single-cell structure of fuel cell schematic diagram of the invention；
Fig. 2 is that the anti-carbon metal-supported solid oxide fuel-cell single-cell section realized according to present invention preparation is shown
Micro-structure figure.
In all the appended drawings, identical appended drawing reference is used to indicate identical structure, in which: 1- porous catalytic reformation layer,
2- porous metals supporting layer, 3- porous anode functional layer, 4- dense electrolyte layer, 5- porous cathode layer.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, not
For limiting the present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below that
Not constituting conflict between this can be combined with each other.
As shown in Figure 1, anti-carbon metal-supported solid oxide fuel cell of the invention includes successively combining closely
Porous catalytic reforms layer 1, porous metals supporting layer 2, porous anode functional layer 3, dense electrolyte layer 4 and porous cathode layer 5.
Wherein: the porous catalytic is reformed layer and is mainly made of Ni-M alloy and storage oxygen-water suction oxide；The porous metals supporting layer
Mainly it is made of Ni-M alloy and MgO；The porous anode functional layer mainly by Ni-M alloy and fluorite or Ni-M alloy and
Perovskite structure oxide composition；Wherein the M element is one or more of Fe, Co, Cu, Sn.
Storage oxygen-water suction the oxide is alkaline earth or rear-earth-doped CeO2Base, BaCeO3Base, BaZrO3Base, La2Ce2O7
One or more of oxides such as base.The quality of the MgO is the 0.05-0.1% of the porous metals supporting layer quality；It is excellent
Choosing, the porous catalytic reform layer with a thickness of 20 μm -40 μm, porosity 40%-60%；Preferably, the porous gold
Belong to supporting layer with a thickness of 500 μm -1000 μm, porosity 40%-60%；Preferably, the thickness of the porous anode functional layer
Degree is 10 μm -20 μm, porosity 40%-60%；Preferably, the dense electrolyte layer with a thickness of 10 μm -20 μm；It is preferred that
, the porous cathode layer with a thickness of 5 μm -20 μm, porosity 40%-60%.
Other side according to the invention provides a kind of preparation of anti-carbon metal-supported solid oxide fuel cell
Method, comprising the following steps:
S1 dehydrated alcohol is uniformly mixed with dimethylbenzene and dispersing agent is added as solvent, by the first presoma, pore-creating dosage form
At mixed powder ball milling after the solvent is added, sequentially add plasticizer, first binder and defrother ball milling again, form stream
Prolong slurry, the tape casting after de-bubble, be supported voxel base layer after dry；The first binder is polyvinyl alcohol contracting fourth
Aldehyde；The quality of the MgO powder is the 0.05%-0.1% of the first forerunner weight.
S2 is by the second presoma and fluorite structure oxide or the second presoma and ionic conduction type perovskite structure oxygen
Compound is uniformly mixed, and the second binder is added, the slurry of anode functional layer is obtained after grinding, by the slurry of the anode functional layer
It is printed on the supporter biscuit and anode functional layer thick film biscuit layer is made；Second binder is the pine of ethyl cellulose
Oleyl alcohol, wherein the mass fraction of the ethyl cellulose is 3.5%-4.5%, in the slurry of the anode functional layer, institute
The content for stating the second binder is 30wt.%-40wt.%, the fluorite or ionic conduction type perovskite structure oxide and the
The mass ratio of two presomas is 3:7-4:6.
The second binder is added in electrolyte oxide powder by S3, the slurry of electrolyte layer is obtained after grinding, by the electricity
The slurry of solution matter layer, which is printed on anode functional layer thick film biscuit layer, is made electrolyte layer thick film biscuit layer；The electrolyte layer
Slurry in, the content of second binder is 30wt.%-40wt.%.
S4 will above-mentioned manufactured successively close contact supporter biscuit layer, anode functional layer thick film biscuit layer and electrolyte layer
Thick film biscuit layer degreasing, sintering in air atmosphere, are then cooled to room temperature, obtain the half-cell of metal oxide support；Institute
The time for stating degreasing is 4h-6h, and the temperature of the sintering is 1400 DEG C -1500 DEG C, speed sintering heating and cooled
Rate is 0.5 DEG C/min-5 DEG C/min.
S5 mixes electron conductive type perovskite structure oxide and electrolyte powder, the second binder is added, after grinding
The slurry of cathode functional is obtained, the slurry of the cathode functional is printed onto the electrolyte layer side of the half-cell, is done
It is sintered and cooled room temperature after dry, the monocell of metal oxide support can be obtained；900 DEG C -1100 of the temperature of the sintering
DEG C, the sintering heating and the rate that cools are 3 DEG C/min-5 DEG C/min, described in the slurry of the cathode functional
The content of second binder is 40wt.%-60wt.%.
Third presoma and storage oxygen-water suction oxide powder are uniformly mixed by S6, and the second binder is added, obtains after grinding
Catalysis is made in the support body layer side that the slurry of the catalytic reforming layer is printed onto the monocell by the slurry of catalytic reforming layer
Layer is reformed, in the slurry of the catalytic reforming layer, the content of second binder is 40wt.%-60wt.%, the storage oxygen-
The mass ratio of water suction oxide and the third presoma is 1:9-3:7.
Wherein, first presoma is NiO, MgO and MOx, second presoma is NiO and MOx, before the third
Drive body is NiO and MOx。
Specifically, preparation method of the invention comprises the steps of:
(1) the tape casting prepares supporting layer
Dehydrated alcohol is uniformly mixed according to volume ratio 1:1 as solvent with dimethylbenzene, a certain amount of fish oil conduct is added
Dispersing agent, and stir evenly；By NiO powder, MgO powder and MOxPowder is poured into above-mentioned solvent and is stirred evenly, and starch or carbon dust is added
As pore creating material, ball milling for 24 hours after, sequentially add plasticizer, first binder and defrother, then ball milling forms curtain coating slurry afterwards for 24 hours
Material, the tape casting after froth in vacuum become supporter biscuit after dry, are cut according to required specification；The MgO
Powder accounts for the 0.05%-0.1% of mixed powder quality；The MOxPowder accounts for the 10%-50% of mixed powder quality；The increasing
Modeling agent is BBP(Butyl Benzyl Phthalate (BBP) and poly- alkyl glycol (PAG)；The first binder is polyvinyl butyral
(PVB)；The defrother is cyclohexanone.
(2) silk screen print method prepares anode functional layer
By NiO, MOx, fluorite or ionic conduction type perovskite structure oxide mixed powder, the second binder is added,
The slurry of the anode functional layer is printed onto support voxel using silk screen print method by the slurry that anode functional layer is obtained after grinding
Anode functional layer thick film biscuit is made on base；Second binder is the ethyl of cellulose content 3wt.%-5wt.%
Cellulose terpineol solution；The content of second binder is 30wt.%-40wt.%；The fluorite or ionic conduction type calcium
Perovskite like structure oxide accounts for the 30-40% of mixed powder quality.
(3) silk screen print method prepares electrolyte layer
The second binder is added in selected electrolyte oxide powder, the slurry of electrolyte layer is obtained after grinding, using silk
The slurry of the electrolyte layer is printed on anode functional layer biscuit and electrolyte layer thick film biscuit is made by net print process；Described
The content of two binders is 30wt.%-40wt.%；The content of the electrolyte oxide powder is 60wt.%-70wt.%.
(4) half-cell sinter molding
Through the resulting half-cell biscuit in above-mentioned steps (1)-(3), in air atmosphere 240 DEG C of degreasing 4-6h, again in 1400-
1500 DEG C of high temperature co-firing knot 4-6h, control heating and rate of temperature fall are 0.5 DEG C/min-5 DEG C/min, are cooled to room temperature, can obtain
The half-cell supported to metal oxide.
(5) silk screen print method prepares cathode layer
By perovskite structure oxide and electrolyte mixed powder with electron conduction, the second binder is added, grinds
The slurry of the cathode functional is printed onto step (4) institute using silk screen print method by the slurry that cathode functional is obtained after mill
The electrolyte side of half-cell is made cathode layer thick film biscuit, it is dry after in air atmosphere 900 DEG C of -1100 DEG C of sintering 2h-
3h, control heating and rate of temperature fall are 3 DEG C/min-5 DEG C/min, are cooled to room temperature, and the list of metal oxide support can be obtained
Battery；The content of second binder is 40wt.%-60wt.%；The electrolyte powder accounts for mixed powder quality
40%-60%.
(6) silk screen print method prepares catalytic reforming layer
By NiO, MOxWith storage oxygen-water suction oxide mixed powder, the second binder is added, obtains catalytic reforming after grinding
The slurry of the catalytic reforming layer is printed onto the supporter of monocell obtained by step (5) using silk screen print method by the slurry of layer
Side；The content of second binder is 40wt.%-60wt.%；Storage oxygen-water suction the oxide powder accounts for mixed powder
The 10%-30% of quality.
Wherein, catalytic reforming layer, supporting layer and anode functional layer collectively form multi-layered anode structure, in battery operating conditions
Lower in-situ reducing forms porous catalytic and reforms layer, porous metals supporting layer and porous anode functional layer；Catalytic reforming layer is through original position
After reduction, in-situ sintering can occur under battery operating conditions, and form good interfacial contact with porous metals supporting layer.
The porous catalytic reformation layer mainly stores up oxygen-water suction oxide by Ni-M alloy and on a small quantity and forms, and the M element is
One or more of Fe, Co, Cu, Sn etc.；Storage oxygen-water suction the oxide is alkaline earth or rear-earth-doped CeO2Base, BaCeO3
Base, BaZrO3Base, La2Ce2O7One or more of oxides such as base.
The porous anode functional layer is mainly by Ni-M alloy and fluorite or ionic conduction type perovskite structure oxide group
At the M element is one or more of Fe, Co, Cu, Sn etc.；The fluorite structure oxide is alkaline earth or rear-earth-doped
ZrO2、CeO2Or La2Ce2O7One or more of；The ionic conduction type perovskite structure oxide is alkaline earth or rare earth
The LaGaO of doping3、BaCeO3Or BaZrO3The one or more of kind.The fluorite structure or ionic conduction type perovskite structure oxygen
The content of compound is 30wt.%-50wt.%, to provide ionic conductivity.The material of the dense electrolyte layer be selected from alkaline earth or
Rear-earth-doped ZrO2、CeO2Or La2Ce2O7、LaGaO3、BaCeO3Or BaZrO3The one or more of kind.The dense electrolyte
Matter layer with a thickness of 10 μm -20 μm, under achievable preparation condition reduce electrolyte layer thickness battery can be effectively reduced
Ohmage.
The porous cathode layer mainly by with electron conduction perovskite structure oxide and electrolyte form,
The perovskite structure oxide with electron conduction is alkaline earth element, transition element or rare earth doped
LaCoO3、SrCoO3、LaFeO3、SrMnO3、SmCoO3One or more of Deng；The electrolyte and above-mentioned electrolysis material
Expect identical.The content of the perovskite structure oxide with electron conduction is 50wt.%-80wt.%.
Embodiment 1
(1) it dehydrated alcohol and each 60ml of dimethylbenzene is measured is uniformly mixed and be used as solvent, 4.5g fish oil is added as dispersing agent,
Weigh 207gNiO powder, 23gFe2O3Powder and 1.15gMgO powder, are added in above-mentioned solvent, add 5g starch as pore creating material,
Ball milling is for 24 hours after mixing evenly；It is poly- to sequentially add 9g BBP(Butyl Benzyl Phthalate (BBP), the poly- alkyl glycol of 9g (PAG), 21g
Vinyl butyral (PVB) and 0.2g cyclohexanone, ball milling is for 24 hours after mixing evenly.Gained slurry after ball milling is subjected to froth in vacuum
Processing 30 minutes carries out tape casting and drying on casting machine, and the supporter biscuit with a thickness of 1mm is made.
(2) ethyl cellulose is dissolved in terpinol, the ethyl cellulose that cellulose content is 4wt.% is made
Terpineol solution, as preparing, binder used in screen printing sizing agent is spare.
(3) by 1.8gNiO powder and 1.2gCe0.8Gd0.2O2Powder is added in 2g terpineol solution of ethyl cellulose, grinds 1-
2h obtains the slurry of stable uniform, slurry is printed on supporter biscuit using the method for silk-screen printing, anode functional layer is made
Thick film biscuit, step 3 time of repeating print after natural drying；
(4) by 3.4gCe0.8Gd0.2O2Powder is added in 1.6g terpineol solution of ethyl cellulose, and grinding 1-2h is obtained surely
Slurry is printed on anode functional layer biscuit using the method for silk-screen printing and electrolyte layer thick film element is made by fixed uniform slurry
Base, step 3 time of repeating print after natural drying；
(5) through the resulting half-cell biscuit in above-mentioned steps (1)-(4), in air atmosphere 240 DEG C of degreasing 4-6h, exist again
1450 DEG C of high temperature co-firing knot 4h, control heating and rate of temperature fall are 0.5-5 DEG C/min, are cooled to room temperature, and metal oxide is made
The half-cell of support；
(6) by 1.5gLa0.6Sr0.4Co0.2Fe0.8O3Powder and 1gCe0.8Gd0.2O2Powder is added to 2.5g ethyl cellulose pine tar
In alcoholic solution, grinding 1-2h obtains the slurry of stable and uniform, and slurry is printed onto half electricity obtained by step (5) using silk screen print method
Cathode layer thick film biscuit is made in the electrolyte side in pond, step 2 time of repeating print after natural drying, then in air atmosphere
1050 DEG C of sintering 3h, control heating and rate of temperature fall are 3-5 DEG C/min, are cooled to room temperature, and the list of metal oxide support is made
Battery；
(7) by 2.8gNi0.8Cu0.2O powder and 0.7gCe0.8Gd0.2O2Powder is added in 1.5g terpineol solution of ethyl cellulose,
Grinding 1-2h obtains the slurry of stable uniform, and slurry is printed onto the support of monocell obtained by step (6) using silk screen print method
The monocell comprising catalytic reforming layer is made in body side, step of repeating print after natural drying 4-6 times, which can be in work
In-situ reducing becomes the solid oxide fuel cell monocell of metal support under the conditions of work.
Embodiment 2
(1) it dehydrated alcohol and each 60ml of dimethylbenzene is measured is uniformly mixed and be used as solvent, 4.5g fish oil is added as dispersing agent,
Weigh 115gNiO powder, 115gFe2O3Powder and 1.15gMgO powder, are added in above-mentioned solvent, add 5g starch as pore creating material,
Ball milling is for 24 hours after mixing evenly；Sequentially add 11g BBP(Butyl Benzyl Phthalate (BBP), the poly- alkyl glycol of 11g (PAG), 23g
Polyvinyl butyral (PVB) and 0.25g cyclohexanone, ball milling is for 24 hours after mixing evenly.Gained slurry after ball milling is carried out vacuum to remove
Bubble processing 30 minutes, carries out tape casting and drying on casting machine, and the supporter biscuit with a thickness of 1mm is made.
(2) ethyl cellulose is dissolved in terpinol, the ethyl cellulose that cellulose content is 4wt.% is made
Terpineol solution, as preparing, binder used in screen printing sizing agent is spare.
(3) by 1.8gNiO powder and 1.2gCe0.9Sm0.1O2Powder is added in 2g terpineol solution of ethyl cellulose, grinds 1-
2h obtains the slurry of stable uniform, slurry is printed on supporter biscuit using the method for silk-screen printing, anode functional layer is made
Thick film biscuit, step 3 time of repeating print after natural drying；
(4) by 3.4gCe0.9Sm0.1O2Powder is added in 1.6g terpineol solution of ethyl cellulose, and grinding 1-2h is obtained surely
Slurry is printed on anode functional layer biscuit using the method for silk-screen printing and electrolyte layer thick film element is made by fixed uniform slurry
Base, step 3 time of repeating print after natural drying；
(5) through the resulting half-cell biscuit in above-mentioned steps (1)-(4), in air atmosphere 240 DEG C of degreasing 4-6h, exist again
1450 DEG C of high temperature co-firing knot 4h, control heating and rate of temperature fall are 0.5-5 DEG C/min, are cooled to room temperature, and metal oxide is made
The half-cell of support；
(6) by 1.5gBa0.5Sr0.5Co0.8Fe0.2O3Powder and 1gCe0.9Sm0.1O2Powder is added to 2.5g ethyl cellulose pine tar
In alcoholic solution, grinding 1-2h obtains the slurry of stable uniform, and slurry is printed onto half electricity obtained by step (5) using silk screen print method
Cathode layer thick film biscuit is made in the electrolyte side in pond, step 2 time of repeating print after natural drying, then in air atmosphere
900-1100 DEG C of sintering 3h, control heating and rate of temperature fall are 3-5 DEG C/min, are cooled to room temperature, and metal oxide support is made
Monocell；
(7) by 3gNi0.5Cu0.5Fe2O4Powder and 0.5gCe0.9Sm0.1O21.5g terpineol solution of ethyl cellulose is added in powder
In, grinding 1-2h obtains the slurry of stable uniform, and slurry is printed onto the branch of monocell obtained by step (6) using silk screen print method
The monocell comprising catalytic reforming layer is made in support body side, step of repeating print after natural drying 4-6 times, which can be
In-situ reducing becomes the solid oxide fuel cell monocell of metal support under operating condition.
Embodiment 3
(1) it dehydrated alcohol and each 60ml of dimethylbenzene is measured is uniformly mixed and be used as solvent, 4.5g fish oil is added as dispersing agent,
Weigh 184gNiO powder, 46gFe2O3Powder and 1.15gMgO powder, are added in above-mentioned solvent, add 5g starch as pore creating material,
Ball milling is for 24 hours after mixing evenly；Sequentially add 10g BBP(Butyl Benzyl Phthalate (BBP), the poly- alkyl glycol of 10g (PAG), 22g
Polyvinyl butyral (PVB) and 0.23g cyclohexanone, ball milling is for 24 hours after mixing evenly.Gained slurry after ball milling is carried out vacuum to remove
Bubble processing 30 minutes, carries out tape casting and drying on casting machine, and the supporter biscuit with a thickness of 1mm is made.
(2) ethyl cellulose is dissolved in terpinol, the ethyl cellulose that cellulose content is 4wt.% is made
Terpineol solution, as preparing, binder used in screen printing sizing agent is spare.
(3) by 1.8gNiO powder and 1.2gBaZr0.1Ce0.7Y0.1Yb0.1O3Powder is added to 2g terpineol solution of ethyl cellulose
In, grinding 1-2h obtains the slurry of stable uniform, and slurry is printed on supporter biscuit using the method for silk-screen printing and is made
Anode functional layer thick film biscuit, step 3 time of repeating print after natural drying；
(4) by 3.4gBaZr0.1Ce0.7Y0.1Yb0.1O3Powder is added in 1.6g terpineol solution of ethyl cellulose, grinds 1-
2h obtains the slurry of stable uniform, slurry is printed on anode functional layer biscuit using the method for silk-screen printing, electrolyte is made
Thickness membranogen base, step 3 time of repeating print after natural drying；
(5) through the resulting half-cell biscuit in above-mentioned steps (1)-(4), in air atmosphere 240 DEG C of degreasing 4-6h, exist again
1450 DEG C of high temperature co-firing knot 4h, control heating and rate of temperature fall are 0.5-5 DEG C/min, are cooled to room temperature, and metal oxide is made
The half-cell of support；
(6) by 1.5gPrBa0.5Sr0.5Co1.5Fe0.5O6Powder and 1gBaZr0.1Ce0.7Y0.1Yb0.1O3Powder is added to 2.5g ethyl
In cellulose terpineol solution, grinding 1-2h obtains the slurry of stable uniform, and slurry is printed onto step using silk screen print method
(5) cathode layer thick film biscuit is made in the electrolyte side of gained half-cell, then step 2 time of repeating print after natural drying exists
900-1100 DEG C of sintering 3h in air atmosphere, control heating and rate of temperature fall are 3-5 DEG C/min, are cooled to room temperature, and metal is made
The monocell of oxide support；
(7) by 2.8gNi0.8Cu0.2O powder and 0.7gBaZr0.1Ce0.7Y0.1Yb0.1O31.5g ethyl cellulose pine tar is added in powder
In alcoholic solution, grinding 1-2h obtains the slurry of stable uniform, and slurry is printed onto single electricity obtained by step (6) using silk screen print method
The monocell comprising catalytic reforming layer is made in the supporter side in pond, step of repeating print after natural drying 4-6 times, single electricity
Pond in-situ reducing can become the solid oxide fuel cell monocell that metal supports under running conditions.
Embodiment 4
Step (1), (2) in the preparation for the anti-carbon metal-supported solid oxide fuel cell that the present embodiment is related to,
(3), (4), (5), (6) are with embodiment 1, and institute is the difference is that step (7): (7) are by 2.8gNi0.5Cu0.5Fe2O4Powder and
0.7gLa1.95Sm0.05Ce2O7Powder is added in 1.5g terpineol solution of ethyl cellulose, and grinding 1-2h obtains the slurry of stable uniform
Slurry is printed onto the supporter side of monocell obtained by step (6) using silk screen print method, repeated print after natural drying by material
Step 4-6 times, is made the monocell comprising catalytic reforming layer, which in-situ reducing can become metal branch under running conditions
The solid oxide fuel cell monocell of support.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of anti-carbon metal-supported solid oxide fuel cell, which is characterized in that porous including what is successively combined closely
Catalytic reforming layer, porous metals supporting layer, porous anode functional layer, dense electrolyte layer and porous cathode layer, wherein
It includes Ni-M alloy and storage oxygen-water suction oxide that the porous catalytic, which reforms layer,；
The porous metals supporting layer includes Ni-M alloy and MgO；
The porous anode functional layer includes Ni-M alloy and fluorite structure oxide or Ni-M alloy and ionic conduction type calcium
Perovskite like structure oxide；
Wherein the M element is one or more of Fe, Co, Cu, Sn.
2. a kind of anti-carbon metal-supported solid oxide fuel cell according to claim 1, which is characterized in that described
Storing up oxygen-water suction oxide is alkaline earth or rear-earth-doped CeO2Base, BaCeO3Base, BaZrO3Base, La2Ce2O7In the oxides such as base
One or more.
3. a kind of anti-carbon metal-supported solid oxide fuel cell according to claim 1 or 2, which is characterized in that
The quality of the MgO is the 0.05-0.1% of the porous metals supporting layer quality；
Preferably, the porous catalytic reform layer with a thickness of 20 μm -40 μm, porosity 40%-60%；
Preferably, the porous metals supporting layer with a thickness of 500 μm -1000 μm, porosity 40%-60%；
Preferably, the porous anode functional layer with a thickness of 10 μm -20 μm, porosity 40%-60%；
Preferably, the dense electrolyte layer with a thickness of 10 μm -20 μm；
Preferably, the porous cathode layer with a thickness of 5 μm -20 μm, porosity 40%-60%.
4. a kind of preparation method of anti-carbon metal-supported solid oxide fuel cell, which comprises the following steps:
S1 dehydrated alcohol is uniformly mixed with dimethylbenzene, and dispersing agent is added as solvent, the first presoma, pore creating material are formed mixed
It closes powder and ball milling after the solvent is added, sequentially add plasticizer, first binder and defrother ball milling again, form curtain coating slurry
Material, the tape casting after de-bubble, be supported voxel base layer after dry；
S2 is by the second presoma and fluorite structure oxide or the second presoma and ionic conduction type perovskite structure oxide
It is uniformly mixed, the second binder is added, the slurry of anode functional layer is obtained after grinding, the slurry of the anode functional layer is printed
Anode functional layer thick film biscuit layer is made on to the supporter biscuit；
The second binder is added in electrolyte oxide powder by S3, the slurry of electrolyte layer is obtained after grinding, by the electrolyte
The slurry of layer, which is printed on anode functional layer thick film biscuit layer, is made electrolyte layer thick film biscuit layer；
S4 will above-mentioned manufactured successively close contact supporter biscuit layer, anode functional layer thick film biscuit layer and electrolyte layer thick film
Biscuit layer degreasing, sintering in air atmosphere, are then cooled to room temperature, obtain the half-cell of metal oxide support；
S5 mixes electron conductive type perovskite structure oxide and electrolyte powder, and the second binder is added, obtains after grinding
The slurry of the cathode functional is printed onto the electrolyte layer side of the half-cell, after dry by the slurry of cathode functional
It is sintered and cooled room temperature, the monocell of metal oxide support can be obtained；
Third presoma and storage oxygen-water suction oxide powder are uniformly mixed by S6 with second of binder, are catalyzed after grinding
The slurry for reforming layer, is made catalytic reforming for the support body layer side that the slurry of the catalytic reforming layer is printed onto the monocell
Layer.
5. the preparation method according to claim 4, which is characterized in that first presoma is NiO, MgO and MOx, described
Second presoma is NiO and MOx, the third presoma is NiO and MOx, wherein the M element is in Fe, Co, Cu, Sn
It is one or more of.
6. preparation method according to claim 4 or 5, which is characterized in that in step S1, the first binder is poly- second
Enol butyral；
The quality of the MgO powder is the 0.05%-0.1% of the first forerunner weight.
7. according to the described in any item preparation methods of claim 4-6, which is characterized in that in step S2, second binder
For the terpineol solution of ethyl cellulose, wherein the mass fraction of the ethyl cellulose is 3.5%-4.5%,
In the slurry of the anode functional layer, the content of second binder is 30wt.%-40wt.%,
The mass ratio of the fluorite or ionic conduction type perovskite structure oxide and the second presoma is 3: 7-4: 6.
8. according to the described in any item preparation methods of claim 4-7, which is characterized in that in step S3, the electrolyte layer
In slurry, the content of second binder is 30wt.%-40wt.%.
9. according to the described in any item preparation methods of claim 4-8, which is characterized in that in step S4, the time of the degreasing
For 4h-6h, the temperature of the sintering is 1400 DEG C -1500 DEG C, the sintering heating and the rate to cool be 0.5 DEG C/
min-5℃/min；
In step S5,900 DEG C -1100 DEG C of the temperature of the sintering, the sintering heating and the rate that cools be 3 DEG C/
Min-5 DEG C/min, in the slurry of the cathode functional, the content of second binder is 40wt.%-60wt.%.
10. according to the described in any item preparation methods of claim 4-9, which is characterized in that in step S6,
In the slurry of the catalytic reforming layer, the content of second binder is 40wt.%-60wt.%,
The mass ratio of the storage oxygen-water suction oxide and the third presoma is 1: 9-3: 7.
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