CN102593480A - Mixed titanate support solid electrolyte multilayer film of solid oxide fuel cell and manufacturing method thereof - Google Patents
Mixed titanate support solid electrolyte multilayer film of solid oxide fuel cell and manufacturing method thereof Download PDFInfo
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Abstract
The invention relates to a mixed titanate support solid electrolyte multilayer film of a solid oxide fuel cell and a manufacturing method of the mixed tianate support solid electrolyte multilayer film of the solid oxide fuel cell. The multilayer film is formed by a transition layer film and an electrolytic layer film which are sequentially formed through depositing on an anode main electronic conduction phase and a structural framework increase phase; the anode main electronic conduction phase is porous perovskite type mixed titanate composite oxides; and the structural framework increase phase is aluminum oxide or mixed zirconium oxide or mixture of the aluminum oxide and the mixed zirconium oxide. The manufacturing method provided by the invention comprises the steps: combining the casting method and the screen printing method, adopting the casting method to manufacture a support green body, adopting the screen printing method to respectively form the transition layer and the electrolytic layer on the support green body through depositing, and firing the support green body, the transition layer and the electrolytic layer at certain temperature to obtain the multilayer film with different dimensions. Compared with the prior art, the porous anode support formed in the invention keeps stable structure in reducing atmosphere for a long time, has high electronic conductivity, can be subjected to oxidation-reduction circulation for many times, resists carbon deposition and has sulfur resisting property.
Description
Technical field
The present invention relates to the method in a kind of fuel cell technology field, specifically is a kind of SOFC doped titanate support solid electrolytic multi-layer film and preparation method thereof.
Background technology
SOFC (Solid Oxide Fuel Cell; SOFC) be a kind of all solid state power generating device that the chemical energy in the fuel directly is transformed into electric energy through electrochemical reaction; It does not need the transition process through the fuel chemical energy → heat energy of associating → mechanical energy → electric energy; Have many advantages; Wherein outstanding advantage is the broad applicability of fuel, and promptly hydrogen, carbon monoxide and hydrocarbon all can be used as fuel, therefore can adopt multiple hydrocarbon fuels such as hydrogen, carbon monoxide, natural gas, liquefied gas, coal gas, biogas, methyl alcohol and ethanol widely.SOFC has application fields, and it is mainly used and comprises distributed power station, family power station, vehicle accessory power supply, uninterrupted power supply and military power supply etc.The developmental research of SOFC and commercialization have received the generally attention of many countries in the world, generally have an optimistic view of the application prospect of SOFC in the world.At present, the major obstacle of SOFC entering commercialized development is battery system life-span and price.Flat solid oxide fuel cell; Especially intermediate temperature solid oxide fuel cell (500～800 ℃) is the forward position and the focus of the present research of SOFC in the world, and its most outstanding advantage is when guaranteeing high power density; Can use cheap alloys such as stainless steel as metallic interconnect materials; Reduce the requirement that sealing is waited other material, can adopt ceramic cheaply preparation technology, be expected significantly to reduce the material and the manufacturing cost of SOFC.Wherein, (YSZ: yttrium stable zirconium oxide) the anode-supported intermediate temperature solid oxide fuel cell has obtained paying attention to widely Ni-YSZ in recent years in the world; The also existing report of good stack performance; The part unit of research and development has possessed fairly large production capacity, but the problem relevant with thick anode support is not resolved.Fuel such as coal gas gasification, natural gas and biomass gasified gas have common characteristic, and promptly these fuel all contain with methane and are main hydrocarbon and are main impurity with sulfide.Conventional at present anode of solid oxide fuel cell is Ni-YSZ; Ni is desirable hydrogen eelctro-catalyst; But the hydrocarbon key in its meeting catalysis fracture hydrocarbon; When being fuel with dried or low water content hydrocarbon, be prone to cause the deposition of carbon at anode surface, the sulfide in the fuel is prone to make Ni to poison simultaneously, thereby SOFC is damaged by carbon obstruction and sulfur poisoning because of anode in power generation process.The method that adopts at present is that steam reforming process is converted into hydrogen and carbon monoxide with hydrocarbon; Remove sulfide with sulfur method; But will increase the complexity of solid oxide fuel cell power generating system like this, reduce generating efficiency, thereby improve the cost of whole system.In redox cycle; Metallic nickel in the porous anode supporter is oxidized to NiO; Then NiO is reduced into metallic nickel; Porous anode supporter experience change in volume, thus the electrolyte cracking caused, therefore if system breaks down and causes supply of fuel to interrupt being prone to cause because of air gets into the anode chamber causing the Ni-YSZ positive electrode support solid oxide fuel cell to damage.To this, development novel solid anode of oxide fuel cell supporting body structure can be realized the efficient utilization of hydrocarbon fuels, accelerates the business-like process of SOFC.
Literature search through to prior art is found, Chinese patent notification number CN 101515647A, and name is called the patent of " directly hydrocarbon fuel solid oxide fuel cell anti-carbon deposition anode and preparation method ", and the anode material that is adopted consists of xSr
1-1.5yM
yTiO
3-(1-x) CeO
2, x=0.3 in the formula～0.7, y=0.04～0.4; M is La, Y or Sm; The doping of La is 0.2～0.4mol%; The doping of Sr is 0.1～0.3mol%, and the doping of Y is 0.02～0.08mol%, but this composite anode materials is deposited on YSZ or SSZ (SSZ: the scandium stabilizing zirconia) on the electrolyte sheet with form of film; Working temperature is 850～900 ℃, therefore is difficult to be implemented in the application in the intermediate temperature solid oxide fuel cell.In addition; Chinese patent notification number CN1897337A; Name is called the patent of " a kind of anode of solid oxide fuel cell and preparation method "; Introduced with adulterated with Ca and Ti ore chromic acid lanthanum or titanate composite oxides be the anode construction skeleton with main electron conduction mutually, adopt ion infusion process or macromolecule template or sol-gel process or suspended particulate slurry dip coating, at the nano particle anode active material perforated membrane of inside and outside surface preparation one deck micron thickness of porous anode structural framework.But because porous anode structural framework sintering at high temperature, cause being difficult to adopting low cost, high efficiency, can large-scale continuous production pottery become embrane method to carry out the dense electrolyte film preparation.On the one hand, the porous anode structural framework is difficult at high temperature further shrink, and has limited the electrolytic thin-membrane that deposits on it and has shunk fine and close; On the other hand, under electrolytical high temperature sintering condition, will grow up, cause its active reduction at the nanometer anode particle on the inside and outside surface of porous anode structural framework.
Summary of the invention
The object of the invention is exactly for the defective that overcomes above-mentioned prior art existence a kind of high electronic conductivity that has to be provided; Can stand repeatedly the OR circulation; Anti-carbon, and have SOFC doped titanate support solid electrolytic multi-layer film of sulfur tolerance and preparation method thereof.
The object of the invention can be realized through following technical scheme: a kind of SOFC doped titanate support solid electrolytic multi-layer film; It is characterized in that this multilayer film is for deposit transition layer film and electrolytic thin-membrane at anode master electron conduction mutually and on the thick film of structural framework wild phase successively; Described anode master electron conduction is porous Ca-Ti ore type doped titanate composite oxides mutually, and described structural framework wild phase is aluminium oxide or doped zirconia or both mixtures.
The chemical composition of described porous Ca-Ti ore type doped titanate composite oxides is A
1-x-zLn
xTi
1-yB
yO
3, A wherein is an alkali earth metal, comprising: calcium (Ca), strontium (Sr) or barium (Ba); Ln is yttrium (Y) or the lanthanide series of doping A, and lanthanide series comprises: lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), gadolinium (Gd), dysprosium (Dy) or mixed rare-earth elements; B is the transition metal of doped Ti, comprising: manganese (Mn), iron (Fe), nickel (Ni), vanadium (V), niobium (Nb) or molybdenum (Mo); X=0-0.5 in the chemical composition, y=0-0.5, z=0-0.5.
A kind of preparation method of SOFC doped titanate support solid electrolytic multi-layer film is characterized in that this method may further comprise the steps:
(1) adopt spray drying process to carry out the doped titanate material preparation: by the stoichiometry of prepared doped titanic acid salt material; Earlier a certain amount of nitric acid and hydrogen peroxide are mixed, then with yttrium nitrate or group of the lanthanides nitrate, alkaline earth nitrate, metatitanic acid four isopropyl esters and transition metal nitrate according to A
1-x-zLn
xTi
1-yB
yO
3Ratio join in nitric acid and the mixed solution of hydrogen peroxide, stir precursor solution, spray-dried precursor powder, 800～1000 ℃ of calcinings 4～10 hours the doped titanate powder body material; With the absolute ethyl alcohol is medium, with planetary ball mill with 100～400rpm rotating speed to doped titanate powder body material ball milling 18～24 hours, the slurry behind the ball milling is crossed 200～400 mesh sieves and is obtained the doped titanate powder 80～100 ℃ of oven dry;
(2) take by weighing doped titanate powder and the wild phase that step (1) makes; Described wild phase content is 0～50wt%; 20～30wt% by taking by weighing doped titanate powder adds the starch pore former; Add mixed solvent and triethyl phosphate dispersant successively, and carry out the ball milling first time with planetary ball mill;
(3) in the slurry of the ball milling first time, add polyvinyl butyral resin binding agent, dibutyl phthalate and Macrogol 200 plastic agent successively, and carrying out the ball milling second time;
(4) will through the second time ball milling slurry process the supporter green compact; Concrete steps comprise: at first vacuum degassing is handled; On casting machine, regulate the scraper height and carry out curtain coating and process the supporter green compact, dried supporter green compact are cut to required size by desired thickness;
(5) ethyl cellulose is dissolved in processes terpineol solution of ethyl cellulose in the terpinol, and use binding agent as silk screen printing;
(6) will be set by step (1) doped titanate powder of making and doped zirconia mixed powder join in the terpineol solution of ethyl cellulose by 70: 30～40: 60 weight ratio; After grinding, obtain the transition zone slurry, form transition zone on the screen process press transition zone slurry for preparing being deposited on equably on the supporter green compact that step (4) makes;
(7) the doped zirconia powder is joined in the terpineol solution of ethyl cellulose, after grinding, obtain electrolyte slurry, form dielectric substrate on the screen process press electrolyte slurry for preparing being deposited on equably on the transition zone that step (6) makes;
(8) the supporter green compact that above-mentioned (4) step, (6) step and (7) step prepared, transition zone and dielectric substrate process plastic removal sintering processes.
The described wild phase of step (2) is aluminium oxide or doped zirconia or both mixtures; Described wild phase is shaped as graininess or fibrous; Described mixed solvent is meant that butanone and ethanol mix the mixed liquor that obtains by 2: 1 weight ratio proportionings, and the addition of mixed solvent is 6 for the weight ratio with the doped titanate powder: (3-4); The concentration of described triethyl phosphate dispersant is 1～5wt%; Described first time, ball milling was meant: with 6～10 hours mixings of 100～400rpm rotating speed ball milling.
The concentration of the described polyvinyl butyral resin binding agent of step (3) is 10～20wt%; The concentration of described dibutyl phthalate is 4～10wt%; The concentration of described Macrogol 200 plastic agent is 4～10wt%; Described second time, ball milling was meant: with planetary ball mill with 100～400rpm rotating speed, 14～18 hours mixings of ball milling again.
The ethyl cellulose cellulose content is 1～5wt% in the described terpineol solution of ethyl cellulose of step (5).
The described doped zirconia of step (6) is yttria-stabilized zirconia (YSZ) or scandium oxide and ceria stabilized zirconia (10Sc1CeSZ); The weight ratio of described mixed powder and terpineol solution of ethyl cellulose is (1.5～4.0): 1; Described transition region thickness is controlled at 5-10 μ m.
The described doped zirconia of step (7) is yttria-stabilized zirconia (YSZ) or scandium oxide and ceria stabilized zirconia (10Sc1CeSZ); The weight ratio of described doped zirconia powder and terpineol solution of ethyl cellulose is (1.5～4.0): 1.
The described plastic removal sintering processes of step (8) is meant: 600 ℃ of plastic removals 2～4 hours, 1200～1400 ℃ of sintering 2～6 hours, wherein the intensification of plastic removal and sintering and rate of temperature fall were 0.5～5 ℃/min then in the air.
Compared with prior art; SOFC doped titanate based composite ceramic material support solid electrolytic multi-layer film of the present invention can be applicable to pluralities of fuel neatly; Promptly in porous supporting body, add catalyst and the eelctro-catalyst that is applicable to special fuel, deposition cathode has just constituted monocell on dielectric substrate again.Formed porous anode supporter has high electronic conductivity in the medium-term and long-term Stability Analysis of Structures of reducing atmosphere, can stand repeatedly the OR circulation, anti-carbon, and have sulfur tolerance.On the preparation method, The tape casting and silk screen print method are combined; Adopt The tape casting to prepare the supporter green compact; Adopt silk screen print method on the supporter green compact, to deposit transition zone and dielectric substrate respectively; Co-sintering obtains the multilayer film of various different sizes at a certain temperature, but forms the preparation technology of simple, low-cost and scale, has good industrialization prospect.
Description of drawings
Fig. 1 is the micro-structure diagram on the electrolyte 10Sc1CeSZ surface of embodiment 1 preparation;
Fig. 2 is the micro-structure diagram of the multilayer film section of embodiment 1 preparation.
Embodiment
Elaborate in the face of embodiments of the invention down, present embodiment provided detailed execution mode and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
Embodiment 1
(1) with 80 gram La
0.2Sr
0.7TiO
3Add in the ball grinders with 20 gram starch, the 120 gram butanone that add again by 2: 1 weight ratios restrain triethyl phosphates with alcohol mixed solvent and 2, with planetary ball mill with 8 hours mixings of 300rpm rotating speed ball milling.In the slurry of above-mentioned milling mixing, be equipped with 18 gram polyvinyl butyral resins respectively again, and 6 gram dibutyl phthalates and 6 gram Macrogol 200s, with planetary ball mill with 300rpm rotating speed 16 hours mixings of ball milling again.The slurry of above-mentioned last milling mixing is carried out vacuum degassing processing 30 minutes, on casting machine, carry out curtain coating and process La
0.2Sr
0.7TiO
3The supporter green compact, dried supporter green compact thickness is 700 μ m.
(2) ethyl cellulose is dissolved in the terpinol, processes the terpineol solution of ethyl cellulose that the ethyl cellulose cellulose content is 2wt%, to be applied to the deposition of transition zone and dielectric substrate with binding agent as silk screen printing.
(3) with 2.88 gram La
0.2Sr
0.7TiO
3Join in 30 milliliters of terpineol solution of ethyl cellulose with the mixed powder of 5.12 gram YSZ, grind the slurry that obtains stable uniform more than the 2h, on screen process press, prepared slurry is deposited on La equably
0.2Sr
0.7TiO
3On the supporter green compact and form transition zone.
(4) 9 gram 10Sc1CeSZ powders are joined in 27 milliliters of terpineol solution of ethyl cellulose, grind the slurry that obtains stable uniform more than the 2h, form dielectric substrate on the screen process press electrolyte slurry for preparing being deposited on the transition zone equably.
(5) with above-mentioned supporter green compact, transition zone and dielectric substrate 600 ℃ of plastic removals 2 hours in air; Then 1300 ℃ of sintering 4 hours; Control heats up and rate of temperature fall is 2 ℃/min; Be prepared into supporter, transition zone and dielectric substrate, thereby accomplish the preparation of doped titanate support solid electrolytic multi-layer film.
As shown in Figure 1, prepared 10Sc1CeSZ dielectric substrate surface is very fine and close, and intergranule combines fine, though some hole of surface, these holes do not run through electrolytic thin-membrane.
As shown in Figure 2, prepared 10Sc1CeSZ dielectric substrate section is very fine and close, and the thickness of electrolytic thin-membrane is about 18 μ m, though section shows a little holes, these holes all are disconnected; Simultaneously, each interlayer combines closely, and supporter demonstrates pore structure uniformly.
Embodiment 2
(1) carries out La by embodiment 1
0.2Sr
0.7TiO
3Supporter green compact and terpineol solution of ethyl cellulose preparation, and transition zone deposition.
(2) 9 gram YSZ powders are joined in 27 milliliters of terpineol solution of ethyl cellulose, grind the slurry that obtains stable uniform more than the 2h, form dielectric substrate on the screen process press electrolyte slurry for preparing being deposited on the transition zone equably.
(3) carry out supporter green compact, transition zone and dielectric substrate co-sintering by embodiment 1, be prepared into doped titanate support solid electrolytic multi-layer film.
Embodiment 3
(1) with 60 gram La
0.2Sr
0.7TiO
3, 20 the gram Al
2O
3Powder and 20 gram starch add in the ball grinders, and the 120 gram butanone that add again by 2: 1 weight ratios restrain triethyl phosphates with alcohol mixed solvent and 2, with planetary ball mill with 8 hours mixings of 300rpm rotating speed ball milling.In the slurry of above-mentioned milling mixing, be equipped with 18 gram polyvinyl butyral resins respectively again, and 6 gram dibutyl phthalates and 6 gram Macrogol 200s, with planetary ball mill with 300rpm rotating speed 16 hours mixings of ball milling again.The slurry of above-mentioned last milling mixing is carried out vacuum degassing processing 30 minutes, on casting machine, carry out curtain coating and process La
0.2Sr
0.7TiO
3The supporter green compact, dried supporter green compact thickness is 700 μ m.
(2) carry out terpineol solution of ethyl cellulose preparation, transition zone and dielectric substrate deposition by embodiment 1.
(3) carry out supporter green compact, transition zone and dielectric substrate co-sintering by embodiment 1, be prepared into doped titanate and alumina composite ceramic materials for support solid electrolyte multilayer film.
Embodiment 4
(1) with 70 gram La
0.2Sr
0.7TiO
3, 10 gram YSZ powders and 20 gram starch add in the ball grinders, the 120 gram butanone that add again by 2: 1 weight ratios restrain triethyl phosphates with alcohol mixed solvent and 2, with planetary ball mill with 8 hours mixings of 300rpm rotating speed ball milling.In the slurry of above-mentioned milling mixing, be equipped with 18 gram polyvinyl butyral resins respectively again, and 6 gram dibutyl phthalates and 6 gram Macrogol 200s, with planetary ball mill with 300rpm rotating speed 16 hours mixings of ball milling again.The slurry of above-mentioned last milling mixing is carried out vacuum degassing processing 30 minutes, on casting machine, carry out curtain coating and process La
0.2Sr
0.7TiO
3The supporter green compact, dried supporter green compact thickness is 700 μ m.
(2) carry out the terpineol solution of ethyl cellulose preparation by embodiment 1, carry out transition zone and dielectric substrate deposition by embodiment 2.
(3) carry out supporter green compact, transition zone and dielectric substrate co-sintering by embodiment 1, be prepared into doped titanate and doped zirconia composite ceramic material support solid electrolytic multi-layer film.
Embodiment 5
(1) with 70 gram La
0.2Sr
0.7TiO
3, 10 the gram Al
2O
3Fiber and 20 gram starch add in the ball grinders, and the 120 gram butanone that add again by 2: 1 weight ratios restrain triethyl phosphates with alcohol mixed solvent and 2, with planetary ball mill with 8 hours mixings of 300rpm rotating speed ball milling.In the slurry of above-mentioned milling mixing, be equipped with 18 gram polyvinyl butyral resins respectively again, and 6 gram dibutyl phthalates and 6 gram Macrogol 200s, with planetary ball mill with 300rpm rotating speed 16 hours mixings of ball milling again.The slurry of above-mentioned last milling mixing is carried out vacuum degassing processing 30 minutes, on casting machine, carry out curtain coating and process La
0.2Sr
0.7TiO
3The supporter green compact, dried supporter green compact thickness is 700 μ m.
(2) carry out terpineol solution of ethyl cellulose preparation, anode functional layer and dielectric substrate deposition by embodiment 1.
(3) carry out supporter green compact, transition zone and dielectric substrate co-sintering by embodiment 1, be prepared into doped titanate and alumina composite ceramic materials for support solid electrolyte multilayer film.
Embodiment 6
The preparation of SOFC doped titanate based composite ceramic material support solid electrolytic multi-layer membrane structure may further comprise the steps:
The first step, adopt spray drying process to carry out the doped titanate material preparation: by the stoichiometry of prepared doped titanic acid salt material, earlier a certain amount of nitric acid and hydrogen peroxide are mixed, then with lanthanum nitrate, strontium nitrate and metatitanic acid four isopropyl esters according to La
0.5Sr
0.5TiO
3Ratio join in nitric acid and the mixed solution of hydrogen peroxide, stir precursor solution, spray-dried precursor powder, 800 ℃ of calcinings 10 hours the doped titanate powder body material.With the absolute ethyl alcohol is medium, with planetary ball mill with the 100rpm rotating speed to doped titanate powder body material ball milling 24 hours, the slurry behind the ball milling is crossed 200 mesh sieves and is got the doped titanate powder 80 ℃ of oven dry.
Second step, take by weighing a certain amount of doped titanate powder and the wild phase alumina granules that are prepared into set by step; The addition of aluminium oxide is the 50wt% of doped titanate powder weight; 20wt% by taking by weighing doped titanate powder adds the starch pore former; Add mixed solvent (butanone and ethanol were by 2: 1 weight ratio proportionings) and triethyl phosphate dispersant successively; The addition of mixed solvent is 2: 1 for the weight ratio with the doped titanate powder, and the concentration of triethyl phosphate dispersant is 1wt%.And carry out the ball milling first time: with 10 hours mixings of 100rpm rotating speed ball milling with planetary ball mill.
The 3rd step, in the slurry of ball milling for the first time, adding polyvinyl butyral resin binding agent, dibutyl phthalate and Macrogol 200 plastic agent successively; The concentration of polyvinyl butyral resin binding agent is 10wt%; The concentration of dibutyl phthalate is 4wt%; The concentration of Macrogol 200 plastic agent is 4wt%, and carries out the ball milling second time: with planetary ball mill with 100rpm rotating speed 18 hours mixings of ball milling again.
The 4th the step, will through the second time ball milling slurry process the supporter green compact; Concrete steps comprise: at first vacuum degassing is handled; On casting machine, regulate the scraper height and carry out curtain coating and process the supporter green compact, dried supporter green compact are cut to required size by desired thickness.
The 5th goes on foot, ethyl cellulose is dissolved in processes terpineol solution of ethyl cellulose in the terpinol, and uses binding agent as silk screen printing; The ethyl cellulose cellulose content is 1wt% in the described terpineol solution of ethyl cellulose.
The 6th step, will be set by step the doped titanate powder and doped zirconia (yttria-stabilized zirconia (the YSZ)) mixed powder that are prepared into join in the terpineol solution of ethyl cellulose by 70: 30 weight ratio, the weight ratio of described mixed powder and terpineol solution of ethyl cellulose is 1.5: 1; After grinding, obtain the transition zone slurry, form transition zone on the screen process press transition zone slurry for preparing being deposited on the supporter green compact equably, transition region thickness is controlled at 5-10 μ m;
The 7th goes on foot, yttria-stabilized zirconia (YSZ) powder is joined in the terpineol solution of ethyl cellulose; After grinding, obtain electrolyte slurry; The weight ratio of yttria-stabilized zirconia (YSZ) and terpineol solution of ethyl cellulose is 1.5: 1, forms dielectric substrate on the screen process press electrolyte slurry for preparing being deposited on the transition zone equably.
The 8th step, will be above-mentioned the supporter green compact, transition zone and the dielectric substrate process plastic removal sintering processes that prepare of the 4th step, the 6th step and the 7th step: in the air 600 ℃ of plastic removals 2 hours; 1350 ℃ of sintering 4 hours, wherein the intensification of plastic removal and sintering and rate of temperature fall were 1 ℃/min then.
Embodiment 7
The preparation of SOFC doped titanate based composite ceramic material support solid electrolytic multi-layer membrane structure may further comprise the steps:
The first step, adopt spray drying process to carry out the doped titanate material preparation: by the stoichiometry of prepared doped titanic acid salt material, earlier a certain amount of nitric acid and hydrogen peroxide are mixed, then with strontium nitrate, niobium oxalate and metatitanic acid four isopropyl esters according to SrTi
0.9Nb
0.1O
3Ratio join in nitric acid and the mixed solution of hydrogen peroxide, stir precursor solution, spray-dried precursor powder, 1000 ℃ of calcinings 4 hours the doped titanate powder body material.With the absolute ethyl alcohol is medium, with planetary ball mill with the 400rpm rotating speed to doped titanate powder body material ball milling 18 hours, the slurry behind the ball milling is 100 ℃ of oven dry, crosses behind 400 mesh sieves for use.
Second step, take by weighing a certain amount of doped titanate powder and the fibrous doped zirconia YSZ of wild phase that are prepared into set by step; The addition of doped zirconia is the 5wt% of doped titanate powder weight; 30wt% by taking by weighing powder adds the starch pore former; Add mixed solvent (butanone and ethanol were by 2: 1 weight ratio proportionings) and triethyl phosphate dispersant successively; The addition of mixed solvent is 3: 2 for the weight ratio with the doped titanate powder, and the concentration of triethyl phosphate dispersant is 5wt%, and carries out the ball milling first time with planetary ball mill: with 6 hours mixings of 400rpm rotating speed ball milling.
The 3rd step, in the slurry of ball milling for the first time, adding polyvinyl butyral resin binding agent, dibutyl phthalate and Macrogol 200 plastic agent successively; The concentration of polyvinyl butyral resin binding agent is 20wt%; The concentration of dibutyl phthalate is 10wt%; The concentration of Macrogol 200 plastic agent is 10wt%, and carries out the ball milling second time: with planetary ball mill with 400rpm rotating speed 14 hours mixings of ball milling again.
The 4th the step, will through the second time ball milling slurry process the supporter green compact; Concrete steps comprise: at first vacuum degassing is handled; On casting machine, regulate the scraper height and carry out curtain coating and process the supporter green compact, dried supporter green compact are cut to required size by desired thickness.
The 5th goes on foot, ethyl cellulose is dissolved in processes terpineol solution of ethyl cellulose in the terpinol, and uses binding agent as silk screen printing, and the ethyl cellulose cellulose content is 5wt% in the described terpineol solution of ethyl cellulose.
The 6th step, will be set by step the doped titanate that is prepared into and doped zirconia mixed powder join in the terpineol solution of ethyl cellulose by 40: 60 weight ratio; After grinding, obtain the transition zone slurry, form transition zone on the screen process press transition zone slurry for preparing being deposited on the supporter green compact equably; Described doped zirconia is ceria stabilized zirconia (10Sc1CeSZ); The weight ratio of described mixed powder and terpineol solution of ethyl cellulose is 4.0: 1; Described transition region thickness is controlled at 5-10 μ m.
The 7th step, the doped zirconia powder is joined in the terpineol solution of ethyl cellulose, after grinding, obtain electrolyte slurry, on the screen process press electrolyte slurry for preparing is being deposited on the transition zone and the formation dielectric substrate equably; Described doped zirconia is ceria stabilized zirconia (10Sc1CeSZ); The weight ratio of described doped zirconia powder and terpineol solution of ethyl cellulose is 4.0: 1;
The 8th step, will be above-mentioned in the supporter green compact, transition zone and the dielectric substrate process plastic removal sintering processes air that prepare of the 4th step, the 6th step and the 7th step 600 ℃ of plastic removals 2 hours; 1400 ℃ of sintering 4 hours, wherein the intensification of plastic removal and sintering and rate of temperature fall were 2 ℃/min then.
Embodiment 8
A kind of SOFC doped titanate support solid electrolytic multi-layer film, this multilayer film is for deposit transition layer film and electrolytic thin-membrane at anode master electron conduction mutually and on the thick film of structural framework wild phase successively; Described anode master electron conduction is porous Ca-Ti ore type doped titanate composite oxides mutually, and described structural framework wild phase is aluminium oxide or doped zirconia or both mixtures.
The chemical composition of described porous Ca-Ti ore type doped titanate composite oxides is A
1-x-zLn
xTi
1-yB
yO
3, A wherein is calcium (Ca); Ln is the yttrium (Y) of doping calcium (Ca); B is the transition metal manganese (Mn) of doped Ti; X=0.2 in the chemical composition, y=0, z=0.5.All the other are with embodiment 1.
Embodiment 9
A kind of SOFC doped titanate support solid electrolytic multi-layer film, this multilayer film is for deposit transition layer film and electrolytic thin-membrane at anode master electron conduction mutually and on the thick film of structural framework wild phase successively; Described anode master electron conduction is porous Ca-Ti ore type doped titanate composite oxides mutually, and described structural framework wild phase is aluminium oxide or doped zirconia or both mixtures.
The chemical composition of described porous Ca-Ti ore type doped titanate composite oxides is A
1-x-zLn
xTi
1-yB
yO
3, A wherein is barium (Ba); Ln is the lanthanum (La) of doped barium (Ba); B is the transition metal iron (Fe) of doped Ti; X=0.3 in the chemical composition, y=0.5, z=0.All the other are with embodiment 1.
Claims (9)
1. a SOFC doped titanate support solid electrolytic multi-layer film is characterized in that, this multilayer film is for deposit transition layer film and electrolytic thin-membrane at anode master electron conduction mutually and on the thick film of structural framework wild phase successively; Described anode master electron conduction is porous Ca-Ti ore type doped titanate composite oxides mutually, and described structural framework wild phase is aluminium oxide or doped zirconia or both mixtures.
2. a kind of SOFC doped titanate support solid electrolytic multi-layer film according to claim 1 is characterized in that the chemical composition of described porous Ca-Ti ore type doped titanate composite oxides is A
1-x-zLn
xTi
1-yB
yO
3, A wherein is an alkali earth metal, comprising: calcium (Ca), strontium (Sr) or barium (Ba); Ln is yttrium (Y) or the lanthanide series of doping A, and lanthanide series comprises: lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), gadolinium (Gd), dysprosium (Dy) or mixed rare-earth elements; B is the transition metal of doped Ti, comprising: manganese (Mn), iron (Fe), nickel (Ni), vanadium (V), niobium (Nb) or molybdenum (Mo); X=0-0.5 in the chemical composition, y=0-0.5, z=0-0.5.
3. the preparation method of a SOFC doped titanate support solid electrolytic multi-layer film as claimed in claim 1 is characterized in that this method may further comprise the steps:
(1) adopt spray drying process to carry out the doped titanate material preparation: by the stoichiometry of prepared doped titanic acid salt material; Earlier a certain amount of nitric acid and hydrogen peroxide are mixed, then with yttrium nitrate or group of the lanthanides nitrate, alkaline earth nitrate, metatitanic acid four isopropyl esters and transition metal nitrate according to A
1-x-zLn
xTi
1-yB
yO
3Ratio join in nitric acid and the mixed solution of hydrogen peroxide, stir precursor solution, spray-dried precursor powder, 800～1000 ℃ of calcinings 4～10 hours the doped titanate powder body material; With the absolute ethyl alcohol is medium, with planetary ball mill with 100～400rpm rotating speed to doped titanate powder body material ball milling 18～24 hours, the slurry behind the ball milling is crossed 200～400 mesh sieves and is obtained the doped titanate powder 80～100 ℃ of oven dry;
(2) take by weighing doped titanate powder and the wild phase that step (1) makes; Described wild phase content is 0～50wt%; 20～30wt% by taking by weighing doped titanate powder adds the starch pore former; Add mixed solvent and triethyl phosphate dispersant successively, and carry out the ball milling first time with planetary ball mill;
(3) in the slurry of the ball milling first time, add polyvinyl butyral resin binding agent, dibutyl phthalate and Macrogol 200 plastic agent successively, and carrying out the ball milling second time;
(4) will through the second time ball milling slurry process the supporter green compact; Concrete steps comprise: at first vacuum degassing is handled; On casting machine, regulate the scraper height and carry out curtain coating and process the supporter green compact, dried supporter green compact are cut to required size by desired thickness;
(5) ethyl cellulose is dissolved in processes terpineol solution of ethyl cellulose in the terpinol, and use binding agent as silk screen printing;
(6) will be set by step (1) doped titanate powder of making and doped zirconia mixed powder join in the terpineol solution of ethyl cellulose by 70: 30～40: 60 weight ratio; After grinding, obtain the transition zone slurry, form transition zone on the screen process press transition zone slurry for preparing being deposited on equably on the supporter green compact that step (4) makes;
(7) the doped zirconia powder is joined in the terpineol solution of ethyl cellulose, after grinding, obtain electrolyte slurry, form dielectric substrate on the screen process press electrolyte slurry for preparing being deposited on equably on the transition zone that step (6) makes;
(8) the supporter green compact that above-mentioned (4) step, (6) step and (7) step prepared, transition zone and dielectric substrate process plastic removal sintering processes.
4. the preparation method of SOFC doped titanate support solid electrolytic multi-layer film according to claim 3 is characterized in that, the described wild phase of step (2) is aluminium oxide or doped zirconia or both mixtures; Described wild phase is shaped as graininess or fibrous; Described mixed solvent is meant that butanone and ethanol mix the mixed liquor that obtains by 2: 1 weight ratio proportionings, and the addition of mixed solvent is 6 for the weight ratio with the doped titanate powder: (3-4); The concentration of described triethyl phosphate dispersant is 1～5wt%; Described first time, ball milling was meant: with 6～10 hours mixings of 100～400rpm rotating speed ball milling.
5. the preparation method of SOFC doped titanate support solid electrolytic multi-layer film according to claim 3 is characterized in that the concentration of the described polyvinyl butyral resin binding agent of step (3) is 10～20wt%; The concentration of described dibutyl phthalate is 4～10wt%; The concentration of described Macrogol 200 plastic agent is 4～10wt%; Described second time, ball milling was meant: with planetary ball mill with 100～400rpm rotating speed, 14～18 hours mixings of ball milling again.
6. the preparation method of SOFC doped titanate support solid electrolytic multi-layer film according to claim 3 is characterized in that the ethyl cellulose cellulose content is 1～5wt% in the described terpineol solution of ethyl cellulose of step (5).
7. the preparation method of SOFC doped titanate support solid electrolytic multi-layer film according to claim 3; It is characterized in that the described doped zirconia of step (6) is yttria-stabilized zirconia (YSZ) or scandium oxide and ceria stabilized zirconia (10Sc1CeSZ); The weight ratio of described mixed powder and terpineol solution of ethyl cellulose is (1.5～4.0): 1; Described transition region thickness is controlled at 5-10 μ m.
8. the preparation method of SOFC doped titanate support solid electrolytic multi-layer film according to claim 3; It is characterized in that the described doped zirconia of step (7) is yttria-stabilized zirconia (YSZ) or scandium oxide and ceria stabilized zirconia (10Sc1CeSZ); The weight ratio of described doped zirconia powder and terpineol solution of ethyl cellulose is (1.5～4.0): 1.
9. the preparation method of SOFC doped titanate support solid electrolytic multi-layer film according to claim 3; It is characterized in that; The described plastic removal sintering processes of step (8) is meant: in the air 600 ℃ of plastic removals 2～4 hours; 1200～1400 ℃ of sintering 2～6 hours, wherein the intensification of plastic removal and sintering and rate of temperature fall were 0.5～5 ℃/min then.
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