CN102074713A - Anode material for solid oxide fuel cell, preparation method thereof and fuel cell - Google Patents

Anode material for solid oxide fuel cell, preparation method thereof and fuel cell Download PDF

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Publication number
CN102074713A
CN102074713A CN2010105940867A CN201010594086A CN102074713A CN 102074713 A CN102074713 A CN 102074713A CN 2010105940867 A CN2010105940867 A CN 2010105940867A CN 201010594086 A CN201010594086 A CN 201010594086A CN 102074713 A CN102074713 A CN 102074713A
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fuel cell
solid oxide
powder
oxide fuel
anode
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CN102074713B (en
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李永丹
王志明
李红娇
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Tianjin University
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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

Abstract

The invention discloses an anode material for a solid oxide fuel cell. Sr2FexMo2-xO6 with a perofskite crystallographic form is adopted, wherein x is less than or equal to 1 and more than or equal to 1.3, and the anode material is prepared by an EDTA-citric acid complexing method. Sr2FexMo2-xO6 with the perofskite crystallographic form is taken as the anode material to improve the power density and carbon deposition resistance of the solid oxide fuel cell directly taking methane as fuel.

Description

Anode material that a kind of Solid Oxide Fuel Cell is used and preparation method thereof and fuel cell
Technical field
The present invention relates to the fuel cell technology field, specifically, relate to a kind of solid oxide fuel battery system that directly utilizes methane to act as a fuel.
Background technology
Solid Oxide Fuel Cell (SOFC) is that a kind of employing solid material is as electrolyte, it not only has efficiently, outside the eco-friendly characteristics, it also has the not available advantage of other types fuel cell: the battery structure that (1) is all solid state, avoided using corrosion and the electrolyte loss problem that liquid electrolyte brought; (2) energy conversion efficiency height, SOFC at high temperature moves, and its thermal loss can effectively be utilized, if realize cogeneration, its theoretical conversion efficiency of thermoelectric can reach 90%; (3) adaptability to fuel is strong, has gone out outside the hydrogen, can directly use natural gas, and coal gas and other hydrocarbons act as a fuel.
Therefore the direct Solid Oxide Fuel Cell that acts as a fuel with methane has caused the very big interest of domestic and international researcher because operation and equipment are simple.The quantity of pertinent literature of Solid Oxide Fuel Cell utilization of relevant methane, natural gas or other hydro carbons just significantly increases and can be verified from recent years.When methane during as SOFC fuel, because its electro-chemical activity is low, easily form carbon distribution and cause battery performance to reduce fast simultaneously at anode surface, so at present in the world directly the methane fuel battery all also be in conceptual phase, the power density how the focusing on of research improves the SOFC that directly utilizes methane fuel with and long period of operation stability.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, improving is the power density and the anti-carbon performance of the Solid Oxide Fuel Cell of fuel with methane directly, and a kind of Ca-Ti ore type anode material Sr is provided 2Fe xMo 2-xO 6And preparation method thereof.
Another object of the present invention is to overcome deficiency of the prior art, provides a kind of with perovskite-type material Sr 2Fe xMo 2-xO 6Being anode material, is the Solid Oxide Fuel Cell of fuel with methane.
Technical purpose of the present invention is achieved by following technical proposals:
The anode material that a kind of Solid Oxide Fuel Cell is used has the Sr of perovskite crystal formation 2Fe xMo 2-xO 6, 1≤x≤1.3 wherein.
A kind of method for preparing the anode material that Solid Oxide Fuel Cell uses, carry out according to following step:
(1) according to Sr 2Fe xMo 2-xO 6Shown in ratio, dispose the aqueous solution of ferric nitrate and strontium nitrate, the aqueous solution of ammonium molybdate, wherein 1≤x≤1.3 respectively; Wherein the aqueous solution of ammonium molybdate is disposed by following method: at first the method by dropping ammonia is dissolved in ethylenediamine tetra-acetic acid in the deionized water fully, again to wherein adding ammonium molybdate, stirring and dissolving
(2) aqueous solution with ferric nitrate and strontium nitrate adds in the aqueous solution of ammonium molybdate under condition of heating and stirring, add citric acid afterwards, utilize ammoniacal liquor that pH of mixed is transferred to 6.0 again, obtain having the settled solution of color, the mol ratio of each component is an ethylenediamine tetra-acetic acid in the final solution: each metal ion summation: citric acid=1: 1: 1.5
(3) settled solution that step (2) is prepared forms thick gel at 80-120 ℃ of slow heating evaporation under stirring condition;
(4) above-mentioned gel was calcined down 2-5 hour at 200-400 ℃; Grind afterwards, continued calcining 2-6 hour, temperature is 800-1000 ℃
(5) with powder in inert atmosphere, at 1000-1200 ℃ of following calcining 20-40h, the cooling back is taken out and is promptly got anode powder, wherein inert atmosphere is to contain the argon gas of hydrogen or contain the helium of hydrogen or contain the nitrogen of hydrogen, the hydrogen volume mark is 3-10%
Before in inert atmosphere, calcining, can preferably powder be pressed into flaky material, calcine again, take out again after the calcining and grind to form anode powder, for example under the pressure of 200MPa static pressure to become thickness be 1-10mm, diameter is the flaky material of 13-30mm.
A kind of Solid Oxide Fuel Cell is with perovskite crystal formation material Sr 2Fe xMo 2-xO 6As anode material, be fuel gas with methane, 1≤x≤1.3 wherein.
In Solid Oxide Fuel Cell of the present invention, described solid oxide electrolyte can be selected electrolyte commonly used in the field of solid oxide fuel, for example lanthanum strontium gallium magnesium eletrolysis matter; Described cathode material can be selected the cathode material used always, for example a kind of in perovskite-type material lanthanum strontium ferro-cobalt, perovskite-type material strontium ferro-cobalt or the perovskite-type material barium strontium ferro-cobalt.The operating temperature of Solid Oxide Fuel Cell of the present invention is 600-850 ℃.
In the preparation process of battery, can adopt silk screen print method or cladding process among the present invention, be about to cathode powder and anode powder and mix with organic binder bond respectively, adopt silk screen printing or cladding process to form cathode layer and anode layer respectively in the dielectric film both sides.Described organic binder bond is the terpineol solution of ethyl cellulose, and wherein the ethyl cellulose mass ratio is 2-10%.The mass ratio of described cathode powder and organic binder bond is (1: 1)-(3: 1).The mass ratio of described anode powder and organic binder bond is (1: 1)-(3: 1).
Compared with prior art, technical scheme of the present invention adopts perovskite-type material Sr 2Fe xMo 2-xO 6Use as anode material (1≤x≤1.3), with methane is main fuel, utilize high electronic conductivity, ionic conductivity, catalytic activity and the good anti-carbon performance of this perovskite material, make that fuel cell performance is greatly improved when using methane fuel, significantly improved the long period of operation stability of entire cell simultaneously.
Description of drawings
Fig. 1 is the XRD figure of the anode powder of embodiment preparation among the present invention.
Fig. 2 is for utilizing perovskite crystal formation material Sr of the present invention 2Fe xMo 2-xO 6As anode material, the current density-voltage and current density-power density curve of battery when using hydrogen to act as a fuel.(850 ℃ (), 800 ℃ (zero), 750 ℃ (△) following voltage-to-current density curve and 850 ℃ (■), 800 ℃ (●), 750 ℃ (▲) be power density-current density curve down)
Fig. 3 is for utilizing perovskite crystal formation material Sr of the present invention 2Fe xMo 2-xO 6As anode material, the current density-voltage and current density-power density curve of battery when using methane to act as a fuel.(the following voltage-to-current density curve of 850 ℃ (), 800 ℃ (zero) and 850 ℃ (■), 800 ℃ (●) be power density-current density curve down)
Fig. 4 is for utilizing perovskite crystal formation material Sr of the present invention 2Fe xMo 2-xO 6As anode material, when using methane to act as a fuel, the stability curve of battery.
The test battery structural representation of Fig. 5 for being adopted in the embodiment of the invention.
Embodiment
Further specify technical scheme of the present invention below by specific embodiment.
At first utilize the preparation of EDTA-citric acid complex method to have perovskite crystal formation material Sr 2Fe xMo 2-xO 6, 1≤x≤1.3 wherein.
Embodiment 1
(1) takes by weighing Sr (NO 3) 221.269g, Fe (NO 3) 39H 2O 20.508g.Form the transparent metal nitrate solution with deionized water dissolving.Take by weighing EDTA 58.74g, add the 200ml deionized water, under 60 ℃ of stirring in water bath, add 10ml ammoniacal liquor, form clear solution, add (NH afterwards 4) 6Mo 7O 244H 2O 8.917g continues to stir the formation clear solution.Above-mentioned nitrate solution is added the (NH that contains EDTA 4) 6Mo 7O 24In the solution, to wherein adding citric acid C 6H 8O 7H 2O 63.168g.Utilize ammoniacal liquor that above-mentioned pH of mixed is transferred to 6.0, form clear solution.Heating evaporation under 80 ℃ of water-baths afterwards is until forming gel.
(2) institute is formed gel and transfer in the evaporating dish, calcine 4h for 200 ℃ in Muffle furnace, take out grinding afterwards, 900 ℃ of calcining 4h in Muffle furnace take out grinding and form the precursor powder after the cooling again.
(3) with the precursor powder that makes under 200MPa, being pressed into diameter is 20mm, thickness is the disk of 3mm, afterwards disk is put into atmosphere sintering furnace, 1050 ℃ of sintering are 40 hours under the helium atmosphere that contains 8% hydrogen.Take out the cooling back, grinds, and obtains anode powder Sr 2FeMoO 6
Embodiment 2
(1) takes by weighing Sr (NO 3) 221.269g, Fe (NO 3) 39H 2O 26.660g.Form the transparent metal nitrate solution with deionized water dissolving.Take by weighing EDTA 58.74g, add the 200ml deionized water, under 60 ℃ of stirring in water bath, add 10ml ammoniacal liquor, form clear solution, add (NH afterwards 4) 6Mo 7O 244H 2O 6.242g continues to stir the formation clear solution.Above-mentioned nitrate solution is added the (NH that contains EDTA 4) 6Mo 7O 24In the solution, to wherein adding citric acid C 6H 8O 7H 2O 63.168g.Utilize ammoniacal liquor that above-mentioned pH of mixed is transferred to 6.0, form clear solution.Heating evaporation under 80 ℃ of water-baths afterwards is until forming gel.
(2) institute is formed gel and transfer in the evaporating dish, calcine 4h for 200 ℃ in Muffle furnace, take out grinding afterwards, 900 ℃ of calcining 4h in Muffle furnace take out grinding and form the precursor powder after the cooling again.
(3) with the precursor powder that makes under 200MPa, being pressed into diameter is 20mm, thickness is the disk of 3mm, afterwards disk is put into atmosphere sintering furnace, 1050 ℃ of sintering are 48 hours under the argon gas atmosphere that contains 6% hydrogen.Take out the cooling back, grinds, and obtains anode powder Sr 2Fe 1.3Mo 0.7O 6
The anode powder of above-mentioned preparation is carried out Cu target XRD characterize, obtain result such as Fig. 1, by curve among the figure as can be known, the anode powder of preparation presents perovskite crystal formation Sr 2Fe xMo 2-xO 6(wherein 1≤x≤1.3).
Secondly, the perovskite crystal formation Sr that utilizes embodiment to prepare respectively 2Fe xMo 2-xO 6(wherein 1≤x≤1.3) are anode material, assembling fuel cell
(1) takes by weighing the 6g ethyl cellulose, be dissolved in the 95g terpinol, obtain organic binder bond
(2) take by weighing the 8g anode powder, add the 5g organic binder bond, grind and obtain anode slurry
(3) take by weighing 4g barium strontium ferro-cobalt powder, add the 2g organic binder bond, grind cathode slurry
(4) take by weighing 1g lanthanum strontium gallium magnesium dust, to become diameter be the sheet of 20mm to static pressure under 200MPa, afterwards 1450 ℃ of following sintering 20 hours, the cooling back take out polish to thickness be 300 microns, obtain electrolyte sheet
(5) electrolyte sheet one side of utilizing silk screen print method to obtain in above-mentioned steps 7 forms anode layer, afterwards under helium atmosphere, rises to 1100 ℃, sintering 1h with the heating rate of 1 ℃/min
(6) utilize silk screen printing to send out and form cathode layer, afterwards under nitrogen atmosphere, rise to 1000 ℃, sintering 1h with the heating rate of 1 ℃/min at the opposite side of electrolyte sheet
The 3rd, respectively the fuel cell after the assembling is carried out performance test
Anode powder Sr with embodiment 1 preparation 2FeMoO 6Be anode material, carry out performance test, the result is as follows:
(1) with hydrogen be fuel, oxygen is cathode gas, adopts four probe method that above-mentioned fuel cell is tested, and as can be seen from Figure 2, maximum power density is 603mW/cm in the time of 800 ℃ 2
(2) with methane be fuel, oxygen is cathode gas, adopts four probe method that above-mentioned fuel cell is tested, and as can be seen from Figure 3, maximum power density is 429.1mW/cm in the time of 800 ℃ 2
Anode powder Sr with embodiment 2 preparations 2Fe 1.3Mo 0.7O 6Be anode material, carry out performance test, the result is as follows:
(1) with hydrogen be fuel, oxygen is cathode gas, adopts four probe method that above-mentioned fuel cell is tested, and maximum power density can reach 551mW/cm in the time of 800 ℃ 2
(2) with methane be fuel, oxygen is cathode gas, adopts four probe method that above-mentioned fuel cell is tested, and maximum power density can reach 398.3mW/cm in the time of 800 ℃ 2
At last, to the assembling after fuel cell (with Sr 2FeMoO 6, Sr 2Fe 1.3Mo 0.7O 6Be anode material) stability test
Carrying out with methane is fuel, and oxygen is the fuel cell system stability test of cathode gas.Because fuel cell is in the whole service process, under different loads size and the different output current density, the carbon distribution difficulty or ease are different, thus in this test for the stability of the whole fuel cell system of complete reflection, the method for employing loop test.In the concrete test, fuel cell is in begins test under the open circuit voltage, progressively reduce output voltage to 0.3 volt, get back to once more afterwards and begin next circulation under the open circuit voltage.Maximum power density in the each circulation of record is as the index of battery performance in the each circulation of reflection.As Fig. 4 as can be seen, after 20 circulations, maximum power density has only reduced by 5.8%.This shows that the solid oxide fuel battery system of methane that directly utilizes of the present invention has good stable.Simultaneously be worth pointing out the time, test in the present embodiment is in order to reflect the stability of entire cell within a short period of time, adopted continuous loop test method, if battery operates under the big output current density situation all the time, because this moment, carbon distribution trend reduced, fuel battery stability will further be promoted.
More than the present invention has been done exemplary description; should be noted that; under the situation that does not break away from core of the present invention, the replacement that is equal to that any simple distortion, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.

Claims (8)

1. the anode material that Solid Oxide Fuel Cell is used is characterized in that, described material is Sr 2Fe xMo 2-xO 6, 1≤x≤1.3 wherein, and have the perovskite crystal formation.
2. a method for preparing the described anode material of claim 1 is characterized in that, carries out according to following step:
(1) according to Sr 2Fe xMo 2-xO 6Shown in ratio, dispose the aqueous solution of ferric nitrate and strontium nitrate, the aqueous solution of ammonium molybdate, wherein 1≤x≤1.3 respectively; Wherein the aqueous solution of ammonium molybdate is disposed by following method: at first the method by dropping ammonia is dissolved in ethylenediamine tetra-acetic acid in the deionized water fully, again to wherein adding ammonium molybdate, stirring and dissolving
(2) aqueous solution with ferric nitrate and strontium nitrate adds in the aqueous solution of ammonium molybdate under condition of heating and stirring, add citric acid afterwards, utilize ammoniacal liquor that pH of mixed is transferred to 6.0 again, obtain having the settled solution of color, the mol ratio of each component is an ethylenediamine tetra-acetic acid in the final solution: each metal ion summation: citric acid=1: 1: 1.5
(3) settled solution that step (2) is prepared forms thick gel at 80-120 ℃ of slow heating evaporation under stirring condition;
(4) above-mentioned gel was calcined down 2-5 hour at 200-400 ℃; Grind afterwards, continued calcining 2-6 hour, temperature is 800-1000 ℃
(5) with powder in inert atmosphere, at 1000-1200 ℃ of following calcining 20-40h, the cooling back is taken out and is promptly got anode powder, wherein inert atmosphere is to contain the argon gas of hydrogen or contain the helium of hydrogen or contain the nitrogen of hydrogen, the hydrogen volume mark is 3-10%.
3. preparation method according to claim 2 is characterized in that, before calcining in inert atmosphere, powder is pressed into flaky material, calcines again.
4. preparation method according to claim 3 is characterized in that, before calcining in inert atmosphere, to become thickness be 1-10mm to static pressure under the pressure of 200MPa, and diameter is the flaky material of 13-30mm.
5. a Solid Oxide Fuel Cell is characterized in that, described anode material is Sr 2Fe xMo 2-xO 6, 1≤x≤1.3 wherein, and have the perovskite crystal formation; Can be fuel gas with methane simultaneously, under 600-850 ℃, operate.
6. a kind of Solid Oxide Fuel Cell according to claim 5, it is characterized in that, described solid oxide electrolyte is a lanthanum strontium gallium magnesium eletrolysis matter, and described cathode material is a kind of in perovskite-type material lanthanum strontium ferro-cobalt, perovskite-type material strontium ferro-cobalt or the perovskite-type material barium strontium ferro-cobalt.
7. a kind of Solid Oxide Fuel Cell according to claim 5, it is characterized in that, cathode powder and anode powder are mixed with organic binder bond respectively, and described organic binder bond is the terpineol solution of ethyl cellulose, and wherein the ethyl cellulose mass ratio is 2-10%; The mass ratio of described cathode powder and organic binder bond is (1: 1)-(3: 1); The mass ratio of described anode powder and organic binder bond is (1: 1)-(3: 1).
8. the application of anode material as claimed in claim 1 in the Solid Oxide Fuel Cell that with methane is fuel gas.
CN2010105940867A 2010-12-17 2010-12-17 Anode material for solid oxide fuel cell, preparation method thereof and fuel cell Expired - Fee Related CN102074713B (en)

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Cited By (9)

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Publication number Priority date Publication date Assignee Title
CN102290583A (en) * 2011-07-15 2011-12-21 天津大学 Anode material and solid oxide fuel cell utilizing methanol as fuel
CN102633495A (en) * 2012-04-11 2012-08-15 南京大学 Preparation method of room-temperature ferromagnetic Sr2FemMonO6 ceramic
CN103193279A (en) * 2013-04-12 2013-07-10 吉林大学 Method for preparing high electric magnetic resistance material strontium cobalt molybdenum oxide
CN103545537A (en) * 2013-10-30 2014-01-29 上海交通大学 Double-perovskite structure catalyst material for cathode of lithium air battery and preparation method of catalyst material
CN103985888A (en) * 2014-04-15 2014-08-13 淮南师范学院 Preparation method for connection material membrane and electrolyte membrane for ceramic membrane fuel cell
CN112221506A (en) * 2020-09-29 2021-01-15 广州大学 Catalyst, preparation method and application thereof
CN112824326A (en) * 2019-11-20 2021-05-21 中国科学院大连化学物理研究所 A-site-deficient oxide of titanium-based perovskite structure without alkaline earth elements and preparation and application thereof
CN113299934A (en) * 2021-05-13 2021-08-24 中国科学技术大学 Anti-carbon deposition and carbon dioxide resistant fuel electrode material, preparation method thereof and solid oxide cell
CN114042459A (en) * 2021-11-22 2022-02-15 合肥学院 Quasi-dendritic soft magnetic Sr2FeMoO6Preparation method of efficient visible light catalyst

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CN101467286A (en) * 2006-06-13 2009-06-24 日立麦克赛尔株式会社 Fine particle of perovskite oxide, particle having depositedperovskite oxide, catalyst material, catalyst material for oxygen reduction, catalyst material for fuel cell, and electrode for fuel cell
CN101789501A (en) * 2010-01-22 2010-07-28 清华大学 Preparation method for perovskite powder material for cathode of electrolytic tank of solid oxide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101467286A (en) * 2006-06-13 2009-06-24 日立麦克赛尔株式会社 Fine particle of perovskite oxide, particle having depositedperovskite oxide, catalyst material, catalyst material for oxygen reduction, catalyst material for fuel cell, and electrode for fuel cell
CN101789501A (en) * 2010-01-22 2010-07-28 清华大学 Preparation method for perovskite powder material for cathode of electrolytic tank of solid oxide

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102290583A (en) * 2011-07-15 2011-12-21 天津大学 Anode material and solid oxide fuel cell utilizing methanol as fuel
CN102633495A (en) * 2012-04-11 2012-08-15 南京大学 Preparation method of room-temperature ferromagnetic Sr2FemMonO6 ceramic
CN103193279A (en) * 2013-04-12 2013-07-10 吉林大学 Method for preparing high electric magnetic resistance material strontium cobalt molybdenum oxide
CN103545537A (en) * 2013-10-30 2014-01-29 上海交通大学 Double-perovskite structure catalyst material for cathode of lithium air battery and preparation method of catalyst material
CN103985888A (en) * 2014-04-15 2014-08-13 淮南师范学院 Preparation method for connection material membrane and electrolyte membrane for ceramic membrane fuel cell
CN103985888B (en) * 2014-04-15 2017-08-15 淮南师范学院 The preparation method of ceramic membrane fuel cells connecting material film and electrolytic thin-membrane
CN112824326A (en) * 2019-11-20 2021-05-21 中国科学院大连化学物理研究所 A-site-deficient oxide of titanium-based perovskite structure without alkaline earth elements and preparation and application thereof
CN112221506A (en) * 2020-09-29 2021-01-15 广州大学 Catalyst, preparation method and application thereof
CN113299934A (en) * 2021-05-13 2021-08-24 中国科学技术大学 Anti-carbon deposition and carbon dioxide resistant fuel electrode material, preparation method thereof and solid oxide cell
CN114042459A (en) * 2021-11-22 2022-02-15 合肥学院 Quasi-dendritic soft magnetic Sr2FeMoO6Preparation method of efficient visible light catalyst
CN114042459B (en) * 2021-11-22 2024-01-05 合肥学院 Tree-like soft magnetic Sr 2 FeMoO 6 Preparation method of efficient visible light catalyst

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