CN1913208B - Middle-temperature solid oxide fuel cell system material and its cell and preparation method - Google Patents
Middle-temperature solid oxide fuel cell system material and its cell and preparation method Download PDFInfo
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- CN1913208B CN1913208B CN2006100110524A CN200610011052A CN1913208B CN 1913208 B CN1913208 B CN 1913208B CN 2006100110524 A CN2006100110524 A CN 2006100110524A CN 200610011052 A CN200610011052 A CN 200610011052A CN 1913208 B CN1913208 B CN 1913208B
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- 239000000463 material Substances 0.000 title claims abstract description 68
- 239000000446 fuel Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000007787 solid Substances 0.000 title claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 17
- 239000010406 cathode material Substances 0.000 claims abstract description 10
- 239000007790 solid phase Substances 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 26
- 238000005245 sintering Methods 0.000 claims description 19
- 229910017563 LaCrO Inorganic materials 0.000 claims description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- 229910017771 LaFeO Inorganic materials 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 230000003447 ipsilateral effect Effects 0.000 claims description 6
- 239000008393 encapsulating agent Substances 0.000 claims description 5
- 230000005587 bubbling Effects 0.000 claims description 4
- 238000010276 construction Methods 0.000 claims description 3
- 238000007766 curtain coating Methods 0.000 claims description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 2
- 238000007704 wet chemistry method Methods 0.000 claims description 2
- -1 anode Substances 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 13
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
- 239000010405 anode material Substances 0.000 abstract description 7
- 230000010287 polarization Effects 0.000 abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 229910002321 LaFeO3 Inorganic materials 0.000 abstract 2
- 229910002262 LaCrO3 Inorganic materials 0.000 abstract 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 235000011187 glycerol Nutrition 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 6
- 229910002140 La0.6Sr0.4Fe0.8Co0.2O3−δ Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 238000004537 pulping Methods 0.000 description 4
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XPFAJCSMHOQBQB-UHFFFAOYSA-N 2-aminoacetic acid;nitric acid Chemical compound O[N+]([O-])=O.NCC(O)=O XPFAJCSMHOQBQB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 229910002214 La0.9Sr0.1Ga0.8Mg0.2O3−δ Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000004035 construction material Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- XEFGHVQACKIFMS-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;nitric acid Chemical compound O[N+]([O-])=O.OC(=O)CC(O)(C(O)=O)CC(O)=O XEFGHVQACKIFMS-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
This invention relates to a mid-temperature solid oxide fuel battery system material, its battery and its preparation method taking LaCrO3, LaFeO3 and LaFeO3 base materials as the electrolyte of battery system materials, anode and cathode materials and preparing them first by a solid phase or humid chemical method then preparing the battery based on the kind of the supporting structure, and the system has fine comprehensive performance under low and mid temperatures (below 850deg.C), and can be operated in mid temperature; the electrolyte and the electrode materials has good chemistry and heat compatibility, and the battery performance is reduced; the anode materials has good anti-carbon performance, the polarization loss of the cathode is small, the fail-soft operation to the sulfur-containing and nitrogenous fuels is good, and the range of choice to fuel is large, and so on.
Description
Technical field: the present invention relates to a kind of middle temperature solid-oxide fuel system material and battery and preparation method, belong to the energy and material technical field.
Technical background: SOFC (SOFC) is regarded as one of important technology that solves 21st century energy problem because of having efficient, advantages of environment protection.The system material of existing SOFC adopts YSZ (yttria-stabilized zirconia) as electrolyte more, and this material is at (about 1000 ℃) under the very high working temperature, the ionic conducting property that can show; There is serious carbon distribution phenomenon in conventional anode material (like the Ni-electrolyte), causes battery performance to worsen rapidly; Cathode material La commonly used
1-xSr
xMnO
3Under middle low temperature (below 850 ℃) part, show low electronic conductivity, polarization is very big.
Above-mentioned battery operated temperature is too high to be to perplex two subject matters of existing SOFC development with anode carbon distribution phenomenon; The too high meeting of temperature causes that cell sealing difficulty, battery components do not match, performance degradation is rapid, working life is short and problems such as preparation cost height, and anode carbon distribution phenomenon can cause the rapid decay of battery performance and the minimizing in useful life equally.Therefore, the exploitation battery system material that (below 850 ℃) have superperformance in middle low temperature range to reduce the working temperature of SOFC, has crucial meaning.
LaGaO
3The ionic conductivity of sill in the time of 800 ℃ reaches 0.1S/cm; Than traditional electrolyte YSZ (yttria-stabilized zirconia) in the high one magnitude of equal conditions; And in very wide partial pressure of oxygen scope, be pure oxygen ion conductor, be desirable intermediate temperature solid oxide fuel cell (ITSOFC) electrolyte alternative materials.LaCrO
3Sill can solve the carbon distribution phenomenon on the conventional anode material (like the Ni-electrolyte) because of having performances such as high electron-ion conductivity, catalysis, reformation.LaFeO
3Sill is to O
2Have good catalytic activity, its electronic conductivity in the time of 800 ℃ reaches 100～1000S/cm, as its polarization of cathode material much smaller than cathode material La commonly used
1-xSr
xMnO
3Therefore, these materials are very promising ITSOFC materials.But at present people only just study above-mentioned a certain material as the SOFC construction material, still not the report of this three kinds of materials whiles as the system material of a monocell.
Summary of the invention: the objective of the invention is to overcome the deficiency of prior art, a kind of intermediate temperature solid oxide fuel cell system material and battery and preparation method are provided, reduce the working temperature of SOFC.
Technical scheme of the present invention is; This intermediate temperature solid oxide fuel cell (ITSOFC) system material is perovskite (ABO
3) the type electrode material, electrolyte adopts the high LaGaO of ionic conductivity
3Sill, anode material adopt LaCrO
3Sill, negative electrode adopt LaFeO
3Sill; According to actual needs, can in each system material, add doped chemical, and kind and amount through the adjustment doped chemical how much, battery components material coefficient of thermal expansion coefficient is adjusted, making simultaneously has the good chemical compatibility between electrolyte and the electrode material; The doped chemical that adds can be Sr, Ca, Mg, Mn, Co etc., and concrete addition is adjusted according to actual needs, guarantees to have between electrolyte and the electrode material good heat coupling and chemical compatibility to get final product.
This intermediate temperature solid oxide fuel cell (ITSOFC) is made up of electrolyte, anode, cathode systems material and fuel, encapsulant etc., and the electrolyte of battery, anode, cathode material are respectively LaGaO
3Base, LaCrO
3Base, LaFeO
3Based perovskite (ABO
3) type material, the supporting construction of its battery can be electrolyte-supported body structure or cathode support body structure.Electrolyte-supported body structure battery by the two sides respectively sintering porous LaCrO is arranged
3Sill anode layer and LaFeO
3The fine and close LaGaO of sill cathode layer
3Sill electrolyte substrate, with anode | electrolyte | negative electrode assembles in proper order, and fuel (being rich in the gas of hydrogen) such as hydrogen or methane are arranged in the anode, and air or oxygen is arranged in negative electrode.Cathode support body structure battery has fine and close LaGaO by ipsilateral sintering successively
3Sill dielectric substrate and porous LaCrO
3The LaFeO of sill anode layer
3Sill loose structure cathode support body, with anode | electrolyte | negative electrode assembles in proper order, and fuel (being rich in the gas of hydrogen) such as hydrogen or methane are arranged in the anode, and air or oxygen is arranged in negative electrode.
This preparation of solid oxide fuel cell is: adopt traditional solid phase or wet chemistry method (like sol-gel, glycine-nitrate process etc.) to make perovskite (ABO earlier
3) type battery material-LaGaO
3Original washing powder body material, LaCrO
3Original washing powder body material, LaFeO
3Original washing powder body material prepares battery according to the supporting construction type again; If battery adopts the electrolyte-supported structure, then, use LaGaO earlier through traditional press forming and sintering process
3The base material powder body material prepares dense electrolyte supporter substrate, adopts common film techniques such as silk screen and coating again, uses LaCrO
3Sill, LaFeO
3Sill makes the LaCrO of loose structure respectively in the both sides of electrolyte substrate
3Base anode film and LaFeO
3The base cathodic coating, then with anode | electrolyte | the three-in-one composite membrane of negative electrode serve as a basis assembling monocell, again at fuel such as anode feeding hydrogen or methane, at negative electrode bubbling air or oxygen, make intermediate temperature solid oxide fuel cell (ITSOFC); If battery adopts structure for supporting of cathode, then adopt traditional curtain coating or compacting and sintering process earlier, at LaFeO
3Add sintering behind an amount of pore creating material (like active carbon, polyvinyl butyral etc.) and the flow casting molding in the original washing powder body material, process the cathode support body of loose structure, adopt common film techniques such as silk screen and coating again, use LaGaO
3Sill, LaCrO
3Sill, successively the homonymy at cathode support body obtains fine and close LaGaO
3The LaCrO of base electrolyte film and loose structure
3The base anode film, then with anode | electrolyte | the three-in-one composite membrane of negative electrode serve as a basis assembling monocell, again at fuel such as anode feeding hydrogen or methane, at negative electrode bubbling air or oxygen, make intermediate temperature solid oxide fuel cell (ITSOFC).
Above-mentioned perovskite (ABO
3) the type battery material is meant LaGaO
3Sill, LaCrO
3Sill and LaFeO
3Sill; According to actual needs, can be respectively in these materials, add one or more of doped chemical Sr, Ca, Mg, Mn, Co etc., and kind through the adjustment doped chemical and amount how much; Battery components material coefficient of thermal expansion coefficient is adjusted; Make simultaneously the good chemical compatibility arranged between electrolyte and the electrode material that (concrete addition is adjusted according to actual needs, guarantees to have between electrolyte and the electrode material good heat coupling and chemical compatibility to get final product, generally at ABO
3A position in the material and B position add doped chemical, and the molar content of the doped chemical of adding is 10～50%).After adding doped chemical, LaGaO
3Sill can be La
1-xSr
xGa
1-yMg
yO
3-δ, La
1-xSr
xGa
1-y-zMg
yCo
zO
3-δDeng, LaCrO
3Sill can be La
1-xSr
xCr
1-yMn
yO
3-δ, La
1-xCa
xCr
1-yMn
yO
3-δDeng, LaFeO
3Sill can be La
1-xSr
xFe
1-yMn
yO
3-δ, La
1-xSr
xFe
1-yCo
yO
3-δ, La
1-x-ySr
xCa
yFe
1-zCo
zO
3-δDeng.Preparation LaGaO
3Base dense electrolyte supporter substrate or LaFeO
3During Quito pore structure cathode support body; Be shaped and sintering process according to the structural requirement of SOFC electrolyte or cathode support body, the common compacting of adopting such powder body material or curtain coating, the electrolyte-supported body is generally the fine and close substrate of sheet shape, cathode support body is generally loose structure; Because of the conductivity of electrolyte and cathode material all than higher, can prepare the bigger supporter of thickness to obtain the favorable mechanical performance, the outer battery components of supporter all can adopt membrane structure; When filming with common film techniques such as silk screen and coatings; Available ethanol, glycerine and common bond (like polyvinyl butyral, polyvinyl alcohol resin) are filmed the Ca-Ti ore type electrode material pulping (ethanol, glycerine and common bond proportion according to actual needs confirm) that is mixed; Obtain battery pile with connecting material the monocell parallel connection or after connecting, can generate electricity.
Compared with prior art, the advantage that has of the present invention: 1, electrolyte adopts the high LaGaO of ionic conductivity
3Sill can reduce the internal resistance of entire cell; Anode material adopts LaCrO
3Sill can reduce the carbon distribution phenomenon on the conventional anode; Negative electrode adopt conductivity high, to the good LaFeO of oxygen reduction performance
3Sill can significantly reduce the cathodic polarization loss.
2, the construction material of entire cell can be worked under middle temperature, the sealing of battery and material chosen wide ranges such as connect.
3, the material of entire cell all is a perovskite-type material, and temperature has close or identical influence to Effect on Performance such as material crystalline structure transformations, and stability test can be good; Because of anode and negative electrode have ion-electron mixing conductivity, generally do not need to mix therein metal or preparation of electrolyte combination electrode.
4, the good chemical compatibility is arranged between electrolyte and the electrode material; Various battery components material coefficient of thermal expansion coefficients can be according to actual needs, through the kind of doped chemical and how much adjusting of amount.These characteristics are to there being crucial meaning in performance that improves battery and the useful life that prolongs battery.
Electrolyte and electrode material have good chemistry and thermal compatibility, can reduce the decay of battery performance; Anode material anti-carbon performance is good, and is relatively good to the tolerance of sulfur-bearing and nitrogen fuel, can enlarge the range of choice of fuel; The conductivity of cathode material is very high, can reduce the polarization loss of negative electrode.
Description of drawings: the present invention is done further elaboration below in conjunction with accompanying drawing and embodiment.
Fig. 1 is an electrolyte-supported structure battery sketch map of the present invention;
Fig. 2 is a structure for supporting of cathode battery sketch map of the present invention;
Fig. 3 is an electrolyte-supported structure battery preparation technique flow chart of the present invention;
Fig. 4 is a structure for supporting of cathode battery preparation technique flow chart of the present invention.
Among the figure, 1-porous anode film, 2-dense electrolyte supporter, 3-porous cathode film, 4-porous anode film, 5-dense electrolyte film, 6-porous cathode support body.
Embodiment: embodiment 1: like Fig. 1, shown in 3, this intermediate temperature solid oxide fuel cell (ITSOFC) is made up of electrolyte, anode, cathode systems material and fuel, encapsulant etc., adopts the Ca-Ti ore type electrode material, and electrolyte is La
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δMaterial, anode are La
0.7Sr
0.3Cr
0.5Mn
0.5O
3-δMaterial, negative electrode are La
0.6Sr
0.4Fe
0.8Co
0.2O
3-δMaterial.Battery is the electrolyte-supported body structure, by the two sides respectively sintering porous La is arranged
0.7Sr
0.3Cr
0.5Mn
0.5O
3-δAnode layer and La
0.6Sr
0.4Fe
0.8Co
0.2O
3-δThe fine and close La of cathode layer
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δCircular substrate, with anode | electrolyte | negative electrode assembles in proper order, hydrogen is arranged in the anode, air is arranged in negative electrode.
The preparation method of this ITSOFC is: adopt the synthetic La of conventional solid-state method earlier
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δElectrolyte powder material, and the synthetic La of glycine-nitrate process
0.7Sr
0.3Cr
0.5Mn
0.5O
3-δAnode and La
0.6Sr
0.4Fe
0.8Co
0.2O
3-δThe cathode powder material adopts traditional press forming and sintering process, again with La
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δAt 1480 ℃ of following sintering, obtaining diameter is 16mm behind the pressed powder, and thickness is the disc electrolyte-supported body of 0.5mm; Adopt the method for common silk screen printing then, with La
0.7Sr
0.3Cr
0.5Mn
0.5O
3-δAnd La
0.6Sr
0.4Fe
0.8Co
0.2O
3-δPowder body material is about the La of 20 μ m respectively with ethanol, glycerine and the polyvinyl butyral pulping (mass percent of ethanol, glycerine and binding agent is respectively 5%, 10%, 3%) that is mixed at electrolyte-supported body substrate coated on both sides thickness
0.7Sr
0.3Cr
0.5Mn
0.5O
3-δAnode film and La
0.6Sr
0.4Fe
0.8Co
0.2O
3-δCathodic coating (makes the electrode film effective area be 0.5cm
2), and at 1250 ℃ of following sintering, make electrode film entirely attached on the electrolyte-supported body, and be loose structure; Then with anode | electrolyte | the three-in-one composite membrane of negative electrode is a basis assembling monocell, at anode feeding hydrogen, negative electrode bubbling air (air mass flow is 0.5L/min, and hydrogen flowing quantity is 0.5L/min), promptly makes ITSOFC (battery operated temperature is 830 ℃).
The open circuit voltage of this battery is 1.02V, and near theoretical electromotive force, the maximum power density of battery is 300mW/cm
2Behind the battery operation 50h, open circuit voltage and power output do not have obvious decay; The XRD testing result shows that chemical reaction does not all take place for the electrode material of battery and electrolyte in the process of cell preparation and operation.
Embodiment 2: like Fig. 2, shown in 4, this intermediate temperature solid oxide fuel cell (ITSOFC) is made up of electrolyte, anode, cathode systems material and fuel, encapsulant etc., and its electrolyte, anode and negative electrode are used La respectively
0.8Sr
0.2Ga
0.8Mg
0.16Co
0.04O
3-δ, La
0.75Ca
0.25Cr
0.5Mn
0.5O
3-δAnd La
0.6Sr
0.25Ca
0.15Fe
0.7Co
0.3O
3-δPerovskite-type material.Battery is a structure for supporting of cathode, by ipsilateral sintering successively fine and close La is arranged
0.8Sr
0.2Ga
0.8Mg
0.16Co
0.04O
3-δDielectric substrate and porous La
0.75Ca
0.25Cr
0.5Mn
0.5O
3-δThe La of anode layer
0.6Sr
0.25Ca
0.15Fe
0.7Co
0.3O
3-δThe loose structure cathode support body, with anode | electrolyte | negative electrode assembles in proper order, methane is arranged in the anode, oxygen is arranged in negative electrode.
The preparation method of this ITSOFC is: adopt the synthetic La of sol-gel process earlier
0.8Sr
0.2Ga
0.8Mg
0.16Co
0.04O
3-δElectrolyte powder material, La
0.75Ca
0.25Cr
0.5Mn
0.5O
3-δAnode powder body material and La
0.6Sr
0.25Ca
0.15Fe
0.7Co
0.3O
3-δThe cathode powder material adopts traditional press forming and sintering process, again at La
0.6Sr
0.25Ca
0.15Fe
0.7Co
0.3O
3-δThe adding mass percent is 3% active carbon in the powder, and at 1300 ℃ of following sintering, obtaining diameter is that 16mm, thickness are the loose structure cathode support body of 0.8mm, adopts the method for common silk screen printing then, respectively with La after the compression moulding
0.8Sr
0.2Ga
0.8Mg
0.16Co
0.04O
3-δAnd La
0.75Ca
0.25Cr
0.5Mn
0.5O
3-δPowder body material is about the La of 30 μ m with ethanol, glycerine and the polyvinyl alcohol resin pulping (mass percent of ethanol, glycerine and polyvinyl alcohol resin is respectively 5%, 10%, 2%) that is mixed at cathode support body substrate ipsilateral successively coating thickness
0.8Sr
0.2Ga
0.8Mg
0.16Co
0.04O
3-δDielectric film and La
0.75Ca
0.25Cr
0.5Mn
0.5O
3-δAnode film, and, make fine and close dielectric film and porous electrode film successively entirely attached on the cathode support body respectively at 1450 ℃ and 1300 ℃ of following sintering; Then with anode | electrolyte | the three-in-one composite membrane of negative electrode is a basis assembling monocell; Feed methane at anode, (oxygen flow is 0.2L/min at the negative electrode aerating oxygen; Methane flow is 0.5L/min), promptly make intermediate temperature solid oxide fuel cell (battery operated temperature is 850 ℃).
The open circuit voltage of this battery is 0.7V, and the maximum power density of battery is about 200mW/cm
2After battery accumulative total was moved 50h, open circuit voltage and power output did not have obvious decay; The XRD testing result shows that chemical reaction does not all take place for the electrode material of battery and electrolyte in the process of cell preparation and operation, the carbon distribution phenomenon is not obvious on the anode; SEM detects and shows, the physical structure of cathode support body and electrolyte and anode film is all less than worsening.
Embodiment 3: shown in Fig. 2 and 4, this intermediate temperature solid oxide fuel cell is made up of electrolyte, anode, cathode systems material and fuel, encapsulant etc., and its electrolyte, anode and negative electrode are used La respectively
0.9Sr
0.1Ga
0.8Mg
0.16Fe
0.04O
3-δ, La
0.7Sr
0.3Cr
0.5Co
0.5O
3-δAnd La
0.8Sr
0.2Fe
0.6Mn
0.4O
3-δPerovskite-type material.Battery is a structure for supporting of cathode, by ipsilateral order sintering fine and close La is arranged
0.9Sr
0.1Ga
0.8Mg
0.16Fe
0.04O
3-δDielectric substrate and porous La
0.7Sr
0.3Cr
0.5Co
0.5O
3-δThe La of anode layer
0.8Sr
0.2Fe
0.6Mn
0.4O
3-δThe loose structure cathode support body, with anode | electrolyte | negative electrode assembles in proper order, biomass gas is arranged in the anode, oxygen is arranged in negative electrode.
The preparation method of this intermediate temperature solid oxide fuel cell is: adopt the synthetic La of citric acid-nitrate process earlier
0.9Sr
0.1Ga
0.8Mg
0.16Fe
0.04O
3-δElectrolyte powder material, La
0.7Sr
0.3Cr
0.5Co
0.5O
3-δAnode powder body material and La
0.8Sr
0.2Fe
0.6Mn
0.4O
3-δThe cathode powder material.Again at La
0.8Sr
0.2Fe
0.6Mn
0.4O
3-δPowder adds mass fraction and is respectively 10% solvent, 5% active carbon and 3% polyvinyl butyral and flow casting molding, and the oven dry back is at 1300 ℃ of following sintering, and obtaining diameter is that 15mm, thickness are the loose structure cathode support body of 0.8mm, then respectively with La
0.9Sr
0.1Ga
0.8Mg
0.16Fe
0.04O
3-δAnd La
0.7Sr
0.3Cr
0.5Co
0.5O
3-δPowder body material is used ethanol; Glycerine and the polyvinyl butyral pulping (mass percent of ethanol, glycerine and polyvinyl butyral is respectively 5%, 10%, 2%) that is mixed; Adopt the method for silk screen printing again, be about the La of 30 μ m at cathode support body substrate ipsilateral successively coating thickness
0.9Sr
0.1Ga
0.8Mg
0.16Fe
0.04O
3-δDielectric film and La
0.7Sr
0.3Cr
0.5Co
0.5O
3-δAnode film, and, make fine and close dielectric film and porous electrode film successively entirely attached on the cathode support body respectively at 1450 ℃ and 1200 ℃ of following sintering; Then with anode | electrolyte | the three-in-one composite membrane of negative electrode is a basis assembling monocell; Feed biomass gas at anode, (oxygen flow is 0.2L/min at the negative electrode aerating oxygen; The biogas flow is 0.8L/min), promptly make ITSOFC (battery operated temperature is 850 ℃).
The open circuit voltage of this battery is 0.75V, and the maximum power density of battery is about 150mW/cm
2After battery accumulative total was moved 50h, open circuit voltage and power output did not have obvious decay; The XRD testing result shows that chemical reaction does not all take place for the electrode material of battery and electrolyte in the process of cell preparation and operation, anode has kept perovskite structure and carbon distribution phenomenon not obvious; SEM detects and shows, the physical structure of cathode support body and electrolyte and anode film is all less than worsening.
Claims (3)
1. an intermediate temperature solid oxide fuel cell is made up of electrolyte, anode, cathode systems material and fuel, encapsulant, it is characterized in that electrolyte, anode, the cathode material of battery is respectively LaGaO
3Base, LaCrO
3Base, LaFeO
3Based perovskite ABO
3Type material; A kind of or Sr, Ca, Mg, Mn, Co multiple that also contains doped chemical Mn, Co in each electrolyte, anode, the cathode material; The supporting construction of battery is the cathode support body structure; In the A position and B position of each electrolyte, anode, cathode material, the molar content of the doped chemical of adding is 10～50%.
2. intermediate temperature solid oxide fuel cell according to claim 1 is characterized in that cathode support body structure battery has fine and close LaGaO by ipsilateral sintering successively
3Sill dielectric substrate and porous LaCrO
3The LaFeO of sill anode layer
3Sill loose structure cathode support body, with anode | electrolyte | negative electrode assembles in proper order, and hydrogen or methane are arranged in the anode, and air or oxygen is arranged in negative electrode.
3. the described intermediate temperature solid oxide fuel cell preparation method of claim 1 is characterized in that adopting solid phase or wet chemistry method to make Ca-Ti ore type battery material one LaGaO earlier
3Original washing powder body material, LaCrO
3Original washing powder body material, LaFeO
3Original washing powder body material adopts traditional curtain coating or compacting and sintering process earlier, uses LaFeO
3The cathode support body of original washing powder body material preparation loose structure adopts silk screen again and applies common film technique, uses LaGaO
3Original washing powder body material, LaCrO
3Original washing powder body material, successively the homonymy at cathode support body obtains fine and close LaGaO
3The LaCrO of base electrolyte film and loose structure
3The base anode film, then with anode | electrolyte | the three-in-one composite membrane of negative electrode serve as a basis assembling monocell, again at anode feeding hydrogen or methane fuel, at negative electrode bubbling air or oxygen, make intermediate temperature solid oxide fuel cell.
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| CN101304092B (en) * | 2007-05-11 | 2010-09-29 | 中国科学院大连化学物理研究所 | Cathode material of mid-temperature solid-oxide fuel battery and uses thereof |
| CN101794885A (en) * | 2010-03-04 | 2010-08-04 | 黑龙江大学 | Intermediate-temperature solid oxide fuel cell (LSCF) cathode material with brownmillerite structure |
| CN102142564B (en) * | 2011-02-24 | 2014-04-02 | 安徽工业大学 | LaFeO3-base cathode material of sulfur-oxygen fuel cell |
| CN103613105B (en) * | 2013-11-25 | 2016-01-06 | 中国科学院宁波材料技术与工程研究所 | Monocell, its preparation method and application |
| CN106033825B (en) * | 2015-03-17 | 2018-10-19 | 中国科学院宁波材料技术与工程研究所 | A kind of anode-supported type sodium nickel-based battery and preparation method thereof |
| CN106904971B (en) * | 2017-01-23 | 2021-01-01 | 山东科技大学 | Intermediate microwave composite ceramic LaGaO3-TiO2And method for preparing the same |
| CN110010908A (en) * | 2019-04-09 | 2019-07-12 | 深圳市致远动力科技有限公司 | A kind of fuel cell and battery pile |
| CN109980257A (en) * | 2019-04-09 | 2019-07-05 | 深圳市致远动力科技有限公司 | A kind of battery and its preparation process with negative electricity extremely support |
| CN114520356B (en) * | 2020-11-19 | 2024-02-06 | 中国科学院上海硅酸盐研究所 | Proton conductor type reversible solid oxide battery co-fired at one step at low temperature and preparation method thereof |
| CN114944498B (en) * | 2022-05-26 | 2024-07-05 | 西安交通大学 | Integrated connector supported electric symbiotic solid oxide fuel cell/cell stack reactor |
| CN116161752A (en) * | 2023-03-09 | 2023-05-26 | 东莞理工学院 | Preparation method of composite electrode and application of composite electrode in nitrate-containing wastewater |
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