CN103811789A - Solid oxide fuel cell with symmetrical electrodes, and preparation method and application thereof - Google Patents

Solid oxide fuel cell with symmetrical electrodes, and preparation method and application thereof Download PDF

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CN103811789A
CN103811789A CN201210443007.1A CN201210443007A CN103811789A CN 103811789 A CN103811789 A CN 103811789A CN 201210443007 A CN201210443007 A CN 201210443007A CN 103811789 A CN103811789 A CN 103811789A
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porous electrolyte
electrolyte layer
fuel cell
solid oxide
porous
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占忠亮
孟燮
邵乐
韩达
钱继勤
刘雪娇
王绍荣
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Shanghai Institute of Ceramics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

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Abstract

The invention discloses a solid oxide fuel cell with symmetrical electrodes and a preparation method and application thereof. The solid oxide fuel cell has the following symmetrical structure: an electrocatalysis membrane electrode deposited on the inner wall of the pore of a porous electrolyte, a compact electrolyte layer and another electrocatalysis membrane electrode deposited on the inner wall of the pore of the porous electrolyte. The preparation method comprises the following steps: preparing a porous electrolyte/compact electrolyte/porous electrolyte skeleton structure and an electrocatalysis membrane electrode infiltration precursor solution; infiltrating the prepared porous electrolyte/compact electrolyte/porous electrolyte skeleton structure in the electrocatalysis membrane electrode infiltration precursor solution by using an impregnation method; and carrying out heat treatment. The cell provided by the invention has the advantages of good thermal expansion coupling performance, good thermal shock resistance, low cost, a short preparation period, etc.; and when hydrocarbon is used as a fuel, carbon deposition on the positive electrode of the cell can be effectively prevented, and the cell can be used as an electrolytic bath and has commercialization prospects.

Description

A kind of Solid Oxide Fuel Cell with symmetry electrode and its preparation method and application
Technical field
The present invention relates to a kind of novel solid oxide fuel cell and its preparation method and application, specifically, relate to a kind of Solid Oxide Fuel Cell with symmetry electrode and its preparation method and application, belong to Solid Oxide Fuel Cell technical field.
Background technology
Solid Oxide Fuel Cell (SOFC) is a kind of efficient generating apparatus that chemical energy in fuel is converted into electric energy, if adopt the mode of cogeneration, its fuel availability can approach 75% in theory, and fuel availability has also exceeded 50% in the actual battery system having obtained, be converted in electric device at existing fuel, efficiency is the highest (high temperature solid oxide fuel cell-principle, design and application; Subhash, C.Singhal, Kevin Kendall chief editor, Han Minfang etc. translate; The 15th page).And SOFC not only can utilize hydrogen as fuel, also can utilize the hydrocarbon fuel including synthesis gas, alkane.The energy and environmental problem that high fuel availability and broad fuel range of choice face at present for the solution mankind are significant.
But Solid Oxide Fuel Cell at present, especially electrode is prepared aspect, still faces many technological challenges: 1) anode carbon deposition.At present, widely used anode material is metallic nickel, and the good conductivity of Ni is high to the catalytic activity of fuel, therefore, and with H 2during for fuel, Ni is a kind of excellent anode material.But in the time adopting hydrocarbon fuel, carbon can be adsorbed on metallic nickel particle, makes metallic nickel anode lose at short notice catalytic activity, therefore, the anode material exploration that is applicable to hydrocarbon fuel is imperative.2) thermal matching of material.Because SOFC relates to high-temperature calcination process in traditional electrode preparation, if therefore between adjacent materials thermal coefficient of expansion do not mate, easy generating electrodes obscission in preparation and use procedure, the torsional deformation that seriously even may cause battery with break.And in fact, multiple electrode material thermal coefficient of expansion and the electrolyte with high catalytic activity differs greatly, the thermal matching of traditional electrode preparation process requires to make these high-performance electrodes be difficult to be applied.
U.S. Patent application US2011189582A1 discloses a kind of symmetry electrode material Sr that can be used for preparing SOFC 2fe 2-Xmo xo 6synthetic method, and provide a kind of SOFC structure of applying above-mentioned material, wherein using this material simultaneously as cell cathode and anode, solved a difficult problem for galvanic anode carbon deposition.But in this patent application,, by utilizing silk screen print method to prepare symmetry electrode, electrode catalyst activity is low; And battery is take electrolyte as supporter, and Ohmic resistance is large, these have all hindered the further raising of battery performance.
The electrode dipping technology of preparing developing has in recent years overcome well thermal coefficient of expansion and has not mated the variety of issue causing.There is document to disclose and utilize the tape casting to prepare LSGM (La 0.9sr 0.1ga 0.8mg 0.2o 3) composite ceramic ceramics (the fine and close LSGM| porous of porous LSGM| LSGM), the method anode of recycling liquid phase infiltration soaks NiO, and negative electrode soaks SSC (Sm 0.5sr 0.5coO 3), the battery obtaining is take pure hydrogen as fuel, and air is oxidant, and power output exceedes 1W/cm at 550 ℃ 2.The advantage of this electrode preparation method be electrode after electrolyte high-temperature sintering process, low temperature calcination obtains, and has solved material thermal expansion coefficient and has not mated various difficult problems that cause; And the electrode three-phase reaction interface of liquid infiltration deposition is large, electrode catalyst activity is high.But in above-mentioned battery preparation process, anode and cathode adopts different materials, need to prepare respectively, will definitely avoid anode and cathode material to contact in preparation process, in order to avoid it reacts to each other, affects the catalytic performance of electrode.And for reaching best infiltration amount, infiltration process may also need repeatedly to repeat, the preparation respectively of anode and cathode more will greatly extend the manufacturing cycle of battery, and then has increased battery cost (RSCA dvances, 2 (2012) 4075-4078).
Summary of the invention
For prior art above shortcomings, the object of this invention is to provide a kind of there is good electrical chemical property there is Solid Oxide Fuel Cell of symmetry electrode and its preparation method and application, with the problem such as solve the carbon deposition of galvanic anode and the catalytic activity of oxide electrode is low and impregnated electrode manufacturing cycle is long.
For achieving the above object, the technical solution used in the present invention is as follows:
Have a Solid Oxide Fuel Cell for symmetry electrode, described battery has following symmetrical structure: the electro-catalysis membrane electrode that is deposited on porous electrolyte hole inwall | dense electrolyte layer | be deposited on the electro-catalysis membrane electrode of porous electrolyte hole inwall.
As a kind of preferred version, the material that forms porous electrolyte and dense electrolyte is all selected from doping Y 2o 3zrO 2, doping Sc 2o 3zrO 2, doping Y 2o 3and Sc 2o 3zrO 2, La 1-asr aga 1-bmg bo 3(0.05≤a≤0.30,0.05≤b≤0.30), doping Sm 2o 3ceO 2, doping Gd 2o 3ceO 2, doping Bi 2o 3, doping La 2mo 2o 9, BaZr 0.1ce 0.7y 0.2-cyb co 3(0≤c≤0.20), BaZr 1-dy do 3(0≤d≤0.30) and BaCe 1-em eo 3(M=La, Sm, Pr, Nd, Gd, Zr, Y or Yb; 0≤e≤0.5) in the compound of any one or a few formation.
As a kind of preferred version, the material that forms symmetrical electro-catalysis membrane electrode is all selected from Sr 2fe 1-fmo fo 6, LaSr 2fe 3-gcr go 8, LaSr 2fe 2crO 9, La 1-hsr hsc 1-ife io 3, La 1-hsr hce jfe 1-jo 3, BaZr 0.1ce 0.7y 0.2-kyb ko 3, BaCe 1-mfe mo 3, Ce 1-nsr nvO 3, LaSr 3fe 3-pco po 10, GdBaFe 2-qmo qo 5, BaCo 0.7fe 0.3-rnb ro 3, Ba 0.9co 0.7fe 0.2mo 0.1o 3, LnSr 3-xca xfe 3-yco yo 10, Sm 1-zce zfeO 3in the compound of any one or a few formation, wherein: 0≤f≤1,0≤g≤1,0≤h≤1,0≤i≤0.5,0≤j≤0.5,0≤k≤0.2,0≤m≤0.5,0≤n≤1,0≤p≤3,0≤q≤2,0≤r≤0.3,0≤x≤3,0≤y≤3,0≤z≤0.5; Ln=La or Nd or Gd.
The material that forms symmetrical electro-catalysis membrane electrode can be also the compound that above-mentioned various types of materials and Ag, Au, Pt, Ru, Pd, cerium oxide, doped cerium oxide etc. form.
As a kind of preferred version, the thickness of described dense electrolyte layer is 1～100 μ m.
As a kind of preferred version, the thickness of described porous electrolyte layer is 30～2000 μ m, and the thickness of both sides porous electrolyte layer can be identical, and also can a side thicker, opposite side be thinner.
As a kind of preferred version, the porosity of described porous electrolyte is 5%～95%.
As a kind of preferred version, the thickness of described electro-catalysis membrane electrode is 1 nanometer～1 micron, is densification or loose structure.
As further preferred version, the shared volume fraction of electro-catalysis membrane electrode that is deposited on porous electrolyte hole inwall is 0.1%～99%.
A kind of preparation method of the above-mentioned Solid Oxide Fuel Cell with symmetry electrode, comprises following operation:
A) prepare respectively the slurry of porous electrolyte layer and dense electrolyte layer, two kinds of prepared slurries are carried out respectively to flow casting molding and make porous electrolyte layer and dense electrolyte layer green compact, stacked from bottom to top successively according to porous electrolyte layer/dense electrolyte layer/porous electrolyte layer, then press and obtain plate composite bed green compact altogether, at 1400～1600 ℃, carry out again co-sintering, make plate porous electrolyte | dense electrolyte | porous electrolyte skeleton structure;
B) take the water-soluble inorganic salt of institute's metal ion by the stoichiometric proportion of electro-catalysis thin-film electrode material, add after complexing agent and surfactant soluble in water altogether, preparation electro-catalysis thin-film electrode material infiltration precursor liquid;
C) porous electrolyte step a) being made | dense electrolyte | porous electrolyte skeleton structure is infiltrated in the electro-catalysis thin-film electrode material infiltration precursor liquid that step b) makes 10～30 minutes, then heat-treat at 500～1100 ℃, described in obtaining, there is the Solid Oxide Fuel Cell of symmetry electrode.
The another kind of preparation method of the above-mentioned Solid Oxide Fuel Cell with symmetry electrode, comprises following operation:
1. prepare respectively the slurry of porous electrolyte layer and dense electrolyte layer, utilize extruding-out process that two kinds of prepared slurries are extruded successively according to porous electrolyte layer/dense electrolyte layer/porous electrolyte layer from the inside to the outside, obtain tubular type porous electrolyte layer/dense electrolyte layer/porous electrolyte layer composite bed green compact, at 1400～1600 ℃, carry out again co-sintering, make tubular type porous electrolyte | dense electrolyte | porous electrolyte skeleton structure;
2. take the water-soluble inorganic salt of institute's metal ion by the stoichiometric proportion of electro-catalysis thin-film electrode material, add after complexing agent and surfactant soluble in water altogether, preparation electro-catalysis thin-film electrode material infiltration precursor liquid;
3. the porous electrolyte 1. step being made | dense electrolyte | porous electrolyte skeleton structure is infiltrated in the electro-catalysis thin-film electrode material infiltration precursor liquid that 2. step make 10～30 minutes, then heat-treat at 500～1100 ℃, obtain the described Solid Oxide Fuel Cell with symmetry electrode.
As a kind of preferred version, the formula of size of preparing porous electrolyte layer is as follows:
Figure BDA00002368682900041
The formula of size of preparation dense electrolyte layer is as follows:
Figure BDA00002368682900042
Described solvent is selected from any one or a few in dimethylbenzene, absolute ethyl alcohol, acetone, butanone, butyl acetate; Described dispersant is selected from any one or a few in triethanolamine, acrylic copolymer, methyl anyl alcohol, acrylic resin; Described plasticiser is selected from any one or a few in benzoic ether, polyethylene glycol, dibutyl phthalate; Described binding agent is selected from any one or a few in polyvinyl butyral resin, acrylic resin, epoxy resin; Described pore creating material is selected from any one or a few in graphite, starch, ammonium oxalate, ammonium carbonate.
As another kind of preferred version, the water-soluble inorganic salt of described metal ion is nitrate, chloride, molybdate, vanadate etc.; Described complexing agent is selected from any one or a few in ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, citric acid, urea; Described surfactant is Triton X-100.
The one application of the Solid Oxide Fuel Cell with symmetry electrode of the present invention is as electrolytic cell.
Compared with prior art, the present invention has following beneficial effect:
1) adopt symmetry electrode, thermal expansion matching performance is good, and thermal shock resistance is good;
2) negative electrode active material of positive electrode adopts same material, can realize the synchronous infiltration of anode and cathode, and manufacturing cycle is short;
3) utilize impregnation technology to prepare electro-catalysis membrane electrode, increased reaction interface, improved the catalytic activity of electrode;
4) adopt electro-catalysis thin-films Oxygen compound symmetry electrode, in the time using hydrocarbon fuel, the method that galvanic anode can be oxidized by oxidant is eliminated possible carbon deposition easily.
In sum, the advantages such as a kind of Solid Oxide Fuel Cell with symmetry electrode provided by the invention not only has good thermal expansion matching performance and thermal shock resistance, cost is low, manufacturing cycle is short, and when take hydrocarbon as fuel, can effectively avoid the carbon deposition of galvanic anode, can be used as electrolytic cell, there is good Commercial Prospect.
Accompanying drawing explanation
Fig. 1 is the microscopic appearance of the prepared SOFC with symmetry electrode of embodiment 1 and the SEM photo of structure;
Fig. 2 is the prepared Sr of embodiment 1 2fe 1.5mo 0.5o 6(SFMO) high magnification of membrane electrode amplifies SEM photo;
Fig. 3 is the AC impedance spectrogram of the prepared SOFC with symmetry electrode of embodiment 1 as symmetrical cathode cell different temperatures under air atmosphere;
Fig. 4 is the AC impedance spectrogram of the prepared SOFC with symmetry electrode of embodiment 1 as symmetrical anode cell different temperatures under wet hydrogen atmosphere (moisture 3%);
Fig. 5 is the discharge performance curve of the monocell of the prepared SOFC with symmetry electrode of embodiment 1 when take hydrogen as fuel under different temperatures;
Fig. 6 is the discharge performance curve of the monocell of the prepared SOFC with symmetry electrode of embodiment 1 when take propane as fuel under different temperatures;
Fig. 7 is the discharge performance curve of the monocell of the prepared SOFC with symmetry electrode of embodiment 1 when take hydrogen-propane-hydrogen as fuel at 800 ℃.
Fig. 8 is electrolytic cell (SOEC) described in the embodiment 11 electrolysis I-V curve under 800 ℃ of conditions.
Fig. 9 is electrolytic cell (SOEC) described in the embodiment 11 electrolysis V-t curve under 800 ℃ of conditions.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is further elaborated.
Embodiment 1
A) prepare porous electrolyte | dense electrolyte | porous electrolyte skeleton structure
To La 0.9sr 0.1ga 0.8mg 0.2o 3(LSGM) in electrolyte powder 30g, add successively solvent absolute ethyl alcohol, the each 4g of butanone, dispersant triethanolamine 5g and acrylic copolymer 1g, epoxy resin of binder 5g and plasticizer polyethylene glycol 4g; After mixing, obtain stable homogeneous slurry through ball milling, by slurry vacuum defoamation, remove air in slurry, flow casting molding, obtains dense electrolyte layer green compact;
In LSGM electrolyte powder 30g, add successively solvent absolute ethyl alcohol, the each 4g of butanone, dispersant triethanolamine 5g and acrylic copolymer 1g, epoxy resin of binder 5g, pore creating material ammonium oxalate 20g and plasticizer polyethylene glycol 4g; After mixing, obtain stable homogeneous slurry through ball milling, by slurry vacuum defoamation, remove air in slurry, flow casting molding obtains porous electrolyte layer green compact;
Stacked from bottom to top successively according to porous electrolyte layer/dense electrolyte layer/porous electrolyte layer, then press and obtain composite bed green compact altogether, then at 1500 ℃, carry out co-sintering, make porous electrolyte | dense electrolyte | porous electrolyte skeleton structure;
B) prepare SFMO infiltration precursor liquid
According to Sr 2fe 1.5mo 0.5o 6stoichiometric proportion take respectively strontium nitrate 19g, ferric nitrate 28g and molybdenum pentachloride 6g, be dissolved in 100mL water, add until completely dissolved complexing agent ethylenediamine tetra-acetic acid 53g and surfactant Triton X-1001g, stir, obtain SFMO infiltration precursor liquid;
C) adopt infusion process to prepare SOFC
The porous electrolyte that step a) is made | dense electrolyte | 10min in the SFMO infiltration precursor liquid that porous electrolyte skeleton structure immersion step b) makes, under the driving of capillary force, described SFMO precursor solution through immersion deposition in the hole of porous electrolyte layer inwall, fully dry after again through 500 ℃ of heat treatments 2 hours; Repeat above-mentioned infiltration step, make infiltration amount be about 15%, thereby obtain having the SOFC of symmetry electrode.
Fig. 1 is the microscopic appearance of the prepared SOFC with symmetry electrode of the present embodiment and the SEM photo of structure, as seen from Figure 1: utilize described method successfully to prepare tri-layers of composite electrolyte structure of LSGM, upper and lower two-layer is porous LSGM layer (porosity approximately 40%), it is middle that for fine and close LSGM layer, (thickness is about 30 μ m), the shared porous layer pore volume of infiltration SFMO mark approximately 15%.
Fig. 2 is that the high magnification of the prepared SFMO membrane electrode of the present embodiment amplifies SEM photo, as seen from Figure 2: utilize the method for liquid phase infiltration successfully SFMO to be deposited on to porous LSGM layer hole inwall, the particle diameter of SFMO active particle is about 50nm.
Fig. 3 is the AC impedance spectrogram of the prepared SOFC with symmetry electrode of the present embodiment as symmetrical cathode cell different temperatures under air atmosphere, as seen from Figure 3: the polarization impedance of described battery at 500,550,600,650,700,750,800 ℃ is respectively 6.2,1.9,0.61,0.26,0.14,0.086,0.062 Ω cm 2.
Fig. 4 is the AC impedance spectrogram of the prepared SOFC with symmetry electrode of the present embodiment as symmetrical anode cell different temperatures under wet hydrogen atmosphere (moisture 3%), as seen from Figure 4: the polarization impedance of described battery at 500,550,600,650,700,750,800 ℃ is respectively 5.7,2.3,1.3,0.62,0.37,0.26,0.22 Ω cm 2.
Fig. 5 is the discharge performance curve of the monocell of the prepared SOFC with symmetry electrode of the present embodiment when take hydrogen as fuel under different temperatures, test condition is: anode-side passes into wet hydrogen (moisture 3%), hydrogen flowing quantity is 80mL/min, cathode side passes into compressed air, and air mass flow is 200mL/min; As seen from Figure 5: the battery open circuit voltage of this monocell within the scope of 550～800 ℃ is between 1.096V between 1.008V, and the peak power output at 550,600,650,700,750,800 ℃ is respectively 84,179,349,540,694,776mWcm -2.
Fig. 6 is the discharge performance curve of the monocell of the prepared SOFC with symmetry electrode of the present embodiment when take propane as fuel under different temperatures, test condition is: anode-side passes into wet propane (moisture 3%), propane flow is 40mL/min, cathode side passes into compressed air, and air mass flow is 200mL/min; As seen from Figure 6: the battery open circuit voltage of this battery within the scope of 700～800 ℃ is between 0.84V between 0.96V, and the peak power output at 700,750,800 ℃ is respectively 76,188,326mWcm -2.
Fig. 7 is the discharge performance curve of the monocell of the prepared SOFC with symmetry electrode of the present embodiment when take hydrogen-propane-hydrogen as fuel at 800 ℃, test condition is: anode-side passes into wet hydrogen (moisture 3%), flow is 80mL/min, then switch to wet propane (moisture 3%), flow is 40mL/min, switch to wet hydrogen (moisture 3%), flow is 80mL/min again; As seen from Figure 7: this battery anode regeneration effect after circulation is once good, and at 800 ℃, take hydrogen-propane-hydrogen as fuel, this battery peak power output is respectively 498,326,482mWcm -2.
To sum up experimental result shows, the present embodiment gained battery no matter is as negative electrode or anode uses, and all has preferably chemical property; And all can stablize output as monocell take hydrogen and hydrocarbon as fuel; In addition, while using hydrocarbon fuel, the method that galvanic anode can be oxidized by oxidant is eliminated the carbon deposition that may occur easily.
Embodiment 2
Preparation technology, with embodiment 1, is just changed to electrolyte YSZ (doping 8wt%Y 2o 3zrO 2).Porous YSZ layer porosity approximately 55%, compact YSZ layer thickness approximately 30 μ m.Infiltration SFMO accounts for porous layer pore volume mark and is about 25%.
Test condition is with embodiment 1, during take hydrogen as fuel, open circuit voltage is between 1.021V and 1.07V within the scope of 600～800 ℃ for monocell, and the peak power output at 600,650,700,750,800 ℃ is respectively 78,130,193,250,313mWcm -2between.During take propane as fuel, open circuit voltage is between 0.9V and 0.88V within the scope of 750～800 ℃ for monocell, and the peak power output at 750,800 ℃ is respectively 74,155mWcm -2between.
Embodiment 3
Preparation technology, with embodiment 1, just replaces with electrolyte ScSZ (doping 10wt%Sc 2o 3zrO 2), electro-catalysis thin-film electrode material replaces with LaSr 2fe 2crO 9.
Embodiment 4
Preparation technology, with embodiment 1, just replaces with electrolyte SDC (doping 10wt%Sm 2o 3ceO 2), electro-catalysis thin-film electrode material replaces with LaSr 3fe 1.5co 1.5o 10.
Embodiment 5
Preparation technology, with embodiment 1, just replaces with electrolyte GDC (doping 10wt%Gd 2o 3zrO 2), electro-catalysis thin-film electrode material replaces with BaCo 0.7fe 0.2nb 0.1o 3.
Embodiment 6
Preparation technology, with embodiment 1, just replaces with BaZr by electrolyte 0.8y 0.2o 3, electro-catalysis thin-film electrode material replaces with Ba 0.9co 0.7fe 0.2mo 0.1o 3.
Embodiment 7
Preparation technology, with embodiment 1, just replaces with BaCe by electrolyte 0.8y 0.2o 3, electro-catalysis thin-film electrode material replaces with BaCe 0.2fe 0.8o 3.
Embodiment 8
Preparation technology, with embodiment 1, just replaces with BaCe by electrolyte 0.8yb 0.2o 3, electro-catalysis thin-film electrode material replaces with GdBaFe 1.5mo 0.5o 5.
Embodiment 9
Preparation technology, with embodiment 1, just replaces with (Bi by electrolyte 2o 3) 0.8(Er 2o 3) 0.2, electro-catalysis thin-film electrode material replaces with Sm 0.8ce 0.2feO 3with 10wt%Sm 2o 3doped Ce O 2compound, mass ratio is 70:30.
Embodiment 10
A) prepare tubular type porous electrolyte | dense electrolyte | porous electrolyte skeleton structure
To 8%Y 2o 3stable ZrO 2(YSZ) in electrolyte powder 30g, add successively solvent absolute ethyl alcohol, the each 2.5g of butanone, dispersant triethanolamine 3g and acrylic copolymer 1g, pore creating material ammonium oxalate 20g, epoxy resin of binder 3g and plasticizer polyethylene glycol 3g; After mixing, obtain the slurry 1 of stable homogeneous through ball milling, by slurry vacuum defoamation, remove air in slurry;
To 8%Y 2o 3stable ZrO 2(YSZ) in electrolyte powder 30g, add successively solvent absolute ethyl alcohol, the each 2.5g of butanone, dispersant triethanolamine 3g and acrylic copolymer 1g, epoxy resin of binder 3g and plasticizer polyethylene glycol 3g; After mixing, obtain stable homogeneous slurry 2 through ball milling, by slurry vacuum defoamation, remove air in slurry;
Slurry 2, slurry 1, slurry 2 are extruded onto to conductive electrode outer surface from the inside to the outside successively, form tubular type porous electrolyte | dense electrolyte | porous electrolyte green compact, at 1500 ℃, carry out again co-sintering, make tubular type porous electrolyte | dense electrolyte | porous electrolyte skeleton structure;
B) prepare SFMO infiltration precursor liquid
With step in embodiment 1 b);
C) adopt infusion process to prepare SOFC
With step in embodiment 1 c).
Embodiment 11
Monocell prepared embodiment 2 is used as to electrolytic cell.
Fig. 8 is the electrolysis I-V curve of electrolytic cell under 800 ℃ of conditions described in the present embodiment, test condition: gas flow 500sccm, gas composition 25%H 2-75%H 2o.As seen from Figure 8, curve linear is good, and electrolytic cell open circuit voltage under this test condition is 0.89V.
Fig. 9 is the electrolysis V-t curve of electrolytic cell under 800 ℃ of galvanostatic conditions described in the present embodiment, test condition: gas flow 500sccm, gas composition 25%H 2-75%H 2o, Faradaic current 180mA/cm 2.The hydrogen-producing speed that records electrolytic cell is about 74NmL h -1cm -2(electrode area 84cm 2).As seen from Figure 9, in the 160h of test, it is stable that the voltage of electrolytic cell all keeps, and illustrates that electrolytic cell has good stability.
Finally be necessary described herein: above embodiment is only for being described in more detail technical scheme of the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.

Claims (15)

1. one kind has the Solid Oxide Fuel Cell of symmetry electrode, it is characterized in that, described battery has following symmetrical structure: the electro-catalysis membrane electrode that is deposited on porous electrolyte hole inwall | dense electrolyte layer | be deposited on the electro-catalysis membrane electrode of porous electrolyte hole inwall.
2. the Solid Oxide Fuel Cell with symmetry electrode according to claim 1, is characterized in that: the thickness of described dense electrolyte layer is 1～100 μ m.
3. the Solid Oxide Fuel Cell with symmetry electrode according to claim 1, is characterized in that: the thickness of described porous electrolyte layer is 30～2000 μ m, and the thickness of both sides porous electrolyte layer is identical or different.
4. the Solid Oxide Fuel Cell with symmetry electrode according to claim 1, is characterized in that: the porosity of described porous electrolyte is 5%～95%.
5. the Solid Oxide Fuel Cell with symmetry electrode according to claim 1, is characterized in that: the material that forms porous electrolyte and dense electrolyte is all selected from doping Y 2o 3zrO 2, doping Sc 2o 3zrO 2, doping Y 2o 3and Sc 2o 3zrO 2, La 1-asr aga 1-bmg bo 3, doping Sm 2o 3ceO 2, doping Gd 2o 3ceO 2, doping Bi 2o 3, doping La 2mo 2o 9, BaZr 0.1ce 0.7y 0.2-cyb co 3, BaZr 1-dy do 3and BaCe 1-em eo 3in the compound of any one or a few formation; Wherein: 0.05≤a≤0.30,0.05≤b≤0.30,0≤c≤0.2,0≤d≤0.5,0≤e≤0.5; Described M is selected from any one in La, Sm, Pr, Nd, Gd, Zr, Y and Yb element.
6. the Solid Oxide Fuel Cell with symmetry electrode according to claim 1, is characterized in that: the material that forms symmetrical electro-catalysis membrane electrode is selected from Sr 2fe 1-fmo fo 6, LaSr 2fe 3-gcr go 8, LaSr 2fe 2crO 9, La 1-hsr hsc 1-ife io 3, La 1-hsr hce jfe 1-jo 3, BaZr 0.1ce 0.7y 0.2-kyb ko 3, BaCe 1-mfe mo 3, Ce 1-nsr nvO 3, LaSr 3fe 3-pco po 10, GdBaFe 2-qmo qo 5, BaCo 0.7fe 0.3-rnb ro 3, Ba 0.9co 0.7fe 0.2mo 0.1o 3, LnSr 3-xca xfe 3-yco yo 10, Sm 1-zce zfeO 3in the compound of any one or a few formation, wherein: 0≤f≤1,0≤g≤1,0≤h≤1,0≤i≤0.5,0≤j≤0.5,0≤k≤0.2,0≤m≤0.5,0≤n≤1,0≤p≤3,0≤q≤2,0≤r≤0.3,0≤x≤3,0≤y≤3,0≤z≤0.5; Ln=La or Nd or Gd.
7. the Solid Oxide Fuel Cell with symmetry electrode according to claim 1, is characterized in that: form the material of symmetrical electro-catalysis membrane electrode by Sr 2fe 1-fmo fo 6, LaSr 2fe 3-gcr go 8, LaSr 2fe 2crO 9, La 1-hsr hsc 1-ife io 3, La 1-hsr hce jfe 1-jo 3, BaZr 0.1ce 0.7y 0.2-kyb ko 3, BaCe 1-mfe mo 3, Ce 1-nsr nvO 3, LaSr 3fe 3-pco po 10, GdBaFe 2-qmo qo 5, BaCo 0.7fe 0.3-rnb ro 3, Ba 0.9co 0.7fe 0.2mo 0.1o 3, LnSr 3-xca xfe 3-yco yo 10, Sm 1-zce zfeO 3in any one and Ag, Au, Pt, Ru, Pd, cerium oxide, the compound of any one formation in doped cerium oxide, wherein: 0≤f≤1,0≤g≤1,0≤h≤1,0≤i≤0.5,0≤j≤0.5,0≤k≤0.2,0≤m≤0.5,0≤n≤1,0≤p≤3,0≤q≤2,0≤r≤0.3,0≤x≤3,0≤y≤3,0≤z≤0.5; Ln=La or Nd or Gd.
8. the Solid Oxide Fuel Cell with symmetry electrode according to claim 1, is characterized in that: the shared volume fraction of electro-catalysis membrane electrode that is deposited on porous electrolyte hole inwall is 0.1%～99%.
9. the Solid Oxide Fuel Cell with symmetry electrode according to claim 1, is characterized in that: the thickness of described electro-catalysis membrane electrode is 1 nanometer～1 micron.
10. a method of preparing the Solid Oxide Fuel Cell with symmetry electrode claimed in claim 1, is characterized in that, comprises following operation:
A) prepare respectively the slurry of porous electrolyte layer and dense electrolyte layer, two kinds of prepared slurries are carried out respectively to flow casting molding and make porous electrolyte layer and dense electrolyte layer green compact, stacked from bottom to top successively according to porous electrolyte layer/dense electrolyte layer/porous electrolyte layer, then press and obtain plate composite bed green compact altogether, at 1400～1600 ℃, carry out again co-sintering, make plate porous electrolyte | dense electrolyte | porous electrolyte skeleton structure;
B) take the water-soluble inorganic salt of institute's metal ion by the stoichiometric proportion of electro-catalysis thin-film electrode material, add after complexing agent and surfactant soluble in water altogether, preparation electro-catalysis thin-film electrode material infiltration precursor liquid;
C) porous electrolyte step a) being made | dense electrolyte | porous electrolyte skeleton structure is infiltrated in the electro-catalysis thin-film electrode material infiltration precursor liquid that step b) makes 10～30 minutes, then heat-treat at 500～1100 ℃, obtain the described Solid Oxide Fuel Cell with symmetry electrode.
Prepare the method for the Solid Oxide Fuel Cell with symmetry electrode claimed in claim 1 for 11. 1 kinds, it is characterized in that, comprise following operation:
1. prepare respectively the slurry of porous electrolyte layer and dense electrolyte layer, utilize extruding-out process that two kinds of prepared slurries are extruded successively according to porous electrolyte layer/dense electrolyte layer/porous electrolyte layer from the inside to the outside, obtain tubular type porous electrolyte layer/dense electrolyte layer/porous electrolyte layer composite bed green compact, at 1400～1600 ℃, carry out again co-sintering, make tubular type porous electrolyte | dense electrolyte | porous electrolyte skeleton structure;
2. take the water-soluble inorganic salt of institute's metal ion by the stoichiometric proportion of electro-catalysis thin-film electrode material, add after complexing agent and surfactant soluble in water altogether, preparation electro-catalysis thin-film electrode material infiltration precursor liquid;
3. the porous electrolyte 1. step being made | dense electrolyte | porous electrolyte skeleton structure is infiltrated in the electro-catalysis thin-film electrode material infiltration precursor liquid that 2. step make 10～30 minutes, then heat-treat at 500～1100 ℃, obtain the described Solid Oxide Fuel Cell with symmetry electrode.
12. according to the method described in claim 10 or 11, it is characterized in that, the formula of size of preparing porous electrolyte layer is as follows:
Figure FDA00002368682800021
Figure FDA00002368682800031
The formula of size of preparation dense electrolyte layer is as follows:
Figure FDA00002368682800032
Described solvent is selected from any one or a few in dimethylbenzene, absolute ethyl alcohol, acetone, butanone, butyl acetate; Described dispersant is selected from any one or a few in triethanolamine, acrylic copolymer, methyl anyl alcohol, acrylic resin; Described plasticiser is selected from any one or a few in benzoic ether, polyethylene glycol, dibutyl phthalate; Described binding agent is selected from any one or a few in polyvinyl butyral resin, acrylic resin, epoxy resin; Described pore creating material is selected from any one or a few in graphite, starch, ammonium oxalate, ammonium carbonate.
13. methods according to claim 12, is characterized in that: described electrolyte powder is doping Y 2o 3zrO 2, doping Sc 2o 3zrO 2, doping Y 2o 3and Sc 2o 3zrO 2, La 1-asr aga 1-bmg bo 3, doping Sm 2o 3ceO 2, doping Gd 2o 3ceO 2, doping Bi 2o 3, doping La 2mo 2o 9, BaZr 0.1ce 0.7y 0.2-cyb co 3, BaZr 1-dy do 3and BaCe 1-em eo 3in the compound of any one or a few formation; Wherein: 0.05≤a≤0.30,0.05≤b≤0.30,0≤c≤0.2,0≤d≤0.5,0≤e≤0.5; Described M is selected from any one in La, Sm, Pr, Nd, Gd, Zr, Y and Yb element.
14. according to the method described in claim 10 or 11, it is characterized in that: the water-soluble inorganic salt of described metal ion is any one in nitrate, chloride, molybdate, vanadate; Described complexing agent is selected from any one or a few in ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, citric acid, urea; Described surfactant is Triton X-100.
The Solid Oxide Fuel Cell with symmetry electrode in 15. application rights requirements 1 to 9 described in any one is as electrolytic cell.
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