CN101222060A - Medium-low temperature solid-oxide fuel battery cathode material - Google Patents

Medium-low temperature solid-oxide fuel battery cathode material Download PDF

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Publication number
CN101222060A
CN101222060A CNA2008100557471A CN200810055747A CN101222060A CN 101222060 A CN101222060 A CN 101222060A CN A2008100557471 A CNA2008100557471 A CN A2008100557471A CN 200810055747 A CN200810055747 A CN 200810055747A CN 101222060 A CN101222060 A CN 101222060A
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cathode material
oxide fuel
conductivity
fuel cell
analyzing pure
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赵海雷
滕德强
沈薇
李雪
张翠娟
刘振宇
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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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 relates to a La adulterated solid oxide coated cathode material, wherein, molecular formula of the cathode material is (Ba0.5Sr0.5)1-xLaxCo0.8Fe0.2O3-delta, and x is more than or equal to 0.05 and smaller than or equal to 0.15. The cathode material of the invention has high conductivity in medium and low temperature zones and simultaneously has good chemical stability and thermal stability. The invention can exist stably with CGO under the temperature of 900 DEG C; conductivity of the material under the temperature of 600 DEG C is 08.26S.cm<-1>; compared with materials which are not adulterated with La, the conductivity is raised by 160 percent or so. The invention is suitable for the cathode material of a medium and low temperature solid oxide fuel cell (SOFC).

Description

A kind of intermediate temperature solid oxide fuel cell cathode material
Technical field
The present invention relates to a kind of cathode material, be specifically related to a kind of cathode material for solid-oxide fuel cell.
Background technology
Traditional Solid Oxide Fuel Cell is because its higher operating temperature (about 1000 ℃) has caused its poor stability and short problem of life-span.Reduce the operating temperature of Solid Oxide Fuel Cell at present, the exploitation intermediate temperature solid oxide fuel cell has become one of focus of field of solid oxide fuel research.But along with the reduction of operating temperature, the catalytic activity of negative electrode can significantly reduce.Traditional high-temperature solid oxide battery cathode material La 1-xSr xMnO 3(LSM) because it no longer is applicable to intermediate temperature solid oxide fuel cell in conductivity lower below 800 ℃ and catalytic activity.And the ohmic loss of negative electrode has accounted for very big proportion in the ohmic loss of whole solid oxide fuel battery system, therefore uses high performance cathode material most important for the energy conversion efficiency that improves whole Solid Oxide Fuel Cell.Generally speaking, basic demand for the intermediate temperature solid oxide fuel cell cathode material is: material has higher oxonium ion--electronic conduction ability at middle low-temperature space, good chemical stability and thermal stability also will have and electrolytical Physical Match (thermal coefficient of expansion that is complementary with electrolyte is promptly arranged) simultaneously.Ca-Ti ore type (the ABO that contains cobalt 3) composite mixed oxide is oxonium ion and electronics hybrid conductive material, can be used as potential intermediate temperature solid oxide fuel cell cathode material, but this class cathode material in the research at present all also exists deficiency.The La of perovskite structure for example 0.6Sr 0.4Co 0.2Fe 0.8O 3-δ(LSCF) when middle low temperature, have higher mixed conductivity, but its thermal coefficient of expansion and CGO (Ce 1-xGd xO 2) electrolyte differs bigger, chemical stability is bad simultaneously, and high temperature is down easily and electrolyte generation chemical reaction (L.-W.Tai, M.M.Nasrallah, et al.Structure and electrical properties of La 1-xSr xCo 1-yFe yO 3-δPart 2.Thesystem La 1-xSr xCo 0.2Fe 0.8O 3.Solid State Ionics, 1995 (76): 273-283); With perovskite structure (Ba 0.5Sr 0.5) Co 0.8Fe 0.2O 3-δ(BSCF) performance for the Solid Oxide Fuel Cell of negative electrode is enhanced, but when middle low temperature (Ba 0.5Sr 0.5) Co 0.8Fe 0.2O 3-δConductivity less, and its thermal coefficient of expansion and cerium oxide base electrolyte differ also big (Y.Wang, S.Wang, et al.Performance ofBa 0.5Sr 0.5Co 0.8Fe 0.2O 3-δ-CGO-Ag cathode for IT-SOFCs.J.Alloys Compds.428 (2007) 286).Therefore in order to promote the development of intermediate temperature solid oxide fuel cell, research and development high-performance intermediate temperature solid oxide fuel cell cathode material is necessary and urgent.
Summary of the invention
Provide a kind of new cathode material with perovskite structure for the deficiency of improving existing cathode material, the present invention is doped to (Ba with a spot of La 0.5Sr 0.5) Co 0.8Fe 0.2O 3-δA bit element in, in the hope of improving the conductivity of cathode material, improve the electrolytical chemical compatibility of cathode material and cerium oxide base, and then improve the service behaviour of cathode material, be suitable for intermediate temperature solid oxide fuel cell (SOFC) cathode material.
Concrete technical scheme of the present invention is: a kind of intermediate temperature solid oxide fuel cell cathode material, its ingredient formula is (Ba 0.5Sr 0.5) 1-xLa xCo 0.8Fe 0.2O 3-δ, 0.05≤x≤0.15 wherein.Preferred molecular formula is (Ba 0.5Sr 0.5) 0.9La 0.1Co 0.8Fe 0.2O 3-δThe conductivity of this material in the time of 600 ℃ is 108.26 S.cm -1, the conductivity in the time of 700 ℃ is 87.57S.cm -1, compare Ba 0.5Sr 0.5Co 0.8Fe 0.2O 3-δConductivity under relevant temperature improves about 160%.
Material of the present invention can be synthetic with solid reaction process, also can be synthetic with sol-gel process or coprecipitation.Be the synthetic method that example is introduced material of the present invention below with the solid reaction process.According to the chemical formula ratio of this material, take by weighing the C of stoichiometric proportion respectively 4H 6CoO 44H 2O (analyzing pure), BaCO 3(analyzing pure), SrCO 3(analyzing pure), La 2O 3(analyzing pure), Fe 2O 3(analyzing pure).Above-mentioned material was poured in the ball grinder mix grinding 1-20 hour, used agate ball as abrasive media, alcohol is as dispersant, with the slip drying that mixes.Dried material obtained desired cathode powder material (Ba at 900-1100 ℃ of roasting 5-20 hour 0.5Sr 0.5) 1-xLa xCo 0.8Fe 0.2O 3-δThe inflammable substance that in synthetic cathode material fine powder, adds 10-50% (volume ratio), inflammable substance comprises carbon dust, starch, corn flour, resin, dry-pressing or half-dried molded then in 1100-1300 ℃ of temperature lower calcination 2-16 hour, can prepare the porous cathode block again; Maybe make slurry, adopt silk screen print method its LaGaO that is coated in fine and close stable cerium oxide (CGO) equably or mixes with adding entry, soluble starch and ethyl cellulose in the synthetic cathode material powder 3(the Ba of porous through 800-1000 ℃ of temperature lower calcination 2-16 hour, is made in the electrolyte sheet surface 0.5Sr 0.5) 1-xLa xCo 0.8Fe 0.2O 3-δCathode thin film.
After synthetic powder being added the PVA mixing drying of 0.5-3% (mass ratio), dry-pressing formed in the steel casting mould.The sample bar that is pressed into is warming up to 1000-1200 ℃ in high temperature furnace, is incubated after 5-20 hour, can make fine and close (Ba 0.5Sr 0.5) 1-xLa xCo 0.8Fe 0.2O 3-δThe sample bar is measured conductivity of electrolyte materials by four end leads method.
Beneficial effect:
1. cathode material of the present invention and cerium oxide base electrolyte have good chemical compatibility, and cathode material and CGO electrolyte burn altogether that the X-ray diffraction result shows no significant reaction after 5 hours, as shown in Figure 3.
2. cathode material of the present invention has high oxonium ion and electronic conduction ability, stable conductivity cycle performance, as shown in Figure 2, is particularly suitable for the intermediate temperature solid oxide fuel cell cathode material as cerium oxide base.
With the material of this invention as negative electrode, it is the performance of the battery of negative electrode that CGO is better than under the equal conditions with BSCF as the performance of the battery of electrolyte assembling.
Description of drawings
Fig. 1 adopts solid reaction process at 1100 ℃ of synthetic (Ba 0.5Sr 0.5) 0.9La 0.1Co 0.8Fe 0.2O 3-δThe X-ray diffraction curve spectrum.
Fig. 2 is (Ba 0.5Sr 0.5) 0.9La 0.1Co 0.8Fe 0.2O 3-δThe conductivity variations curve chart of three circulations in 300～900 ℃ of scopes
Fig. 3 is (Ba 0.5Sr 0.5) 0.9La 0.1Co 0.8Fe 0.2O 3-δWith CGO at 900 ℃ of X-ray diffraction curve spectrums after burning 5h altogether.
Fig. 4 is (Ba 0.5Sr 0.5) 0.85La 0.15Co 0.8Fe 0.2O 3-δAt 300～900 ℃ of scope conductivity variations curve charts.
Embodiment
Embodiment 1:0.05mol (Ba 0.5Sr 0.5) 0.9La 0.1Co 0.8Fe 0.2O 3-δSynthetic, the test of conductivity and the test of chemical compatibility.
Take by weighing 4.440g BaCO 3(analyzing pure), 3.322g SrCO 3(analyzing pure), 0.814g La 2O 3(analyzing pure), 0.798g Fe 2O 3(analyzing pure) and 9.963g C 4H 6CoO 44H 2O (analyzing pure).Above-mentioned material ground in ball grinder made it to mix in 8 hours, use agate ball as abrasive media, alcohol is as dispersant.With the slip drying that mixes, dried material obtains desired cathode material (Ba 1100 ℃ of roastings 10 hours 0.5Sr 0.5) 0.9La 0.1Co 0.8Fe 0.2O 3-δMeasuring made powder through the XRD powder diffraction method is cubic perovskite structure, as shown in Figure 1.
Dried material 900 ℃ of pre-burnings after 5 hours, is ground and sieves in (100 order), add the carbon dust of 40% (volume ratio), 2% (volume ratio) PVA solution mixes dry-pressing formedly, and the sample that makes is incubated 5 hours down at 1200 ℃, makes porous cathode material.
Dried material, is ground and sieves in (100 order) after 5 hours 900 ℃ of pre-burnings, and after the PVA mixing drying of adding 1% (mass ratio), dry-pressing formed under the 110MPa, 1100 ℃ of roastings made fine and close cathode material in 10 hours in the air, can be used for conductance measurement.Adopt four end leads method to measure the conductivity of material in 300～900 ℃ of scopes, find that this conductivity of electrolyte materials is far above Ba 0.5Sr 0.5Co 0.8Fe 0.2O 3-δConductivity, the conductivity in the time of 600 ℃ is 108.26 Scm -1Conductivity has only slight decay after three thermal cycles of this cathode material.As shown in Figure 2.
Synthetic cathode material and electrolyte CGO were mixed the back dry-pressing by weight 1: 1 in blocks, is warmed up to 900 ℃ in high temperature furnace, is incubated 5 hours, and the XRD testing result shows this cathode material (Ba 0.5Sr 0.5) 0.9La 0.1Co 0.8Fe 0.2O 3-δBurning altogether with the CGO electrolyte did not have significant reaction after 5 hours, illustrated that both have good chemical compatibility, as shown in Figure 3.
Embodiment 2:0.05mol (Ba 0.5Sr 0.5) 0.95La 0.05Co 0.8Fe 0.2O 3-δSolid reaction process synthetic.
Take by weighing 4.687g BaCO 3(analyzing pure), 3.506g SrCO 3(analyzing pure), 0.407g La 2O 3(analyzing pure), 0.798g Fe 2O 3(analyzing pure) and 9.963g C 4H 6CoO 44H 2O (analyzing pure).Above-mentioned material is poured in the ball grinder, used agate ball as abrasive media, alcohol is as dispersant, and mix grinding is after 8 hours, with the slip drying that mixes.Dried material obtains the cathode material (Ba of cubic perovskite structure 1050 ℃ of roastings 12 hours 0.5Sr 0.5) 0.95La 0.05Co 0.8Fe 0.2O 3-δWith 1050 ℃ of synthetic powders sieve (160 order), cathode material for 1g, add the soluble starch of 10% mass fraction and the ethyl cellulose of 1% mass fraction, add the 1ml deionized water at last, mix the back and be coated in the electrolyte CGO surface of the densification that high temperature burns till with silk screen print method equably, be incubated 5 hours down at 900 ℃, make the porous cathode thin-film material.
Embodiment 3:0.05mol (Ba 0.5Sr 0.5) 0.85La 0.15Co 0.8Fe 0.2O 3-δSolid reaction process synthetic.
Take by weighing 4.193g BaCO 3(analyzing pure), 3.137g SrCO 3(analyzing pure), 1.222g La 2O 3(analyzing pure), 0.798g Fe 2O 3(analyzing pure) and 9.963g C 4H 6CoO 44H 2O (analyzing pure).Above-mentioned material is poured in the ball grinder, used agate ball as abrasive media, alcohol is as dispersant, and mix grinding is after 8 hours, with the slip drying that mixes.Dried material obtains the cathode material (Ba of cubic perovskite structure 1100 ℃ of roastings 10 hours 0.5Sr 0.5) 0.85La 0.15Co 0.8Fe 0.2O 3-δ
Dried material, is ground and sieves in (100 order) after 5 hours 900 ℃ of pre-burnings, and after the PVA mixing drying of adding 1% (mass ratio), dry-pressing formed under the 110MPa, 1100 ℃ of roastings made fine and close cathode material in 10 hours in the air.Adopt four end leads method to measure the conductivity of material in 300～900 ℃ of scopes, find to be increased to 0.15 at the volume of La in the A position, the conductivity of cathode material is significantly improved again, and the conductivity in the time of 600 ℃ is 206.65Scm -1, as shown in Figure 4.
Embodiment 4:0.05mol (Ba 0.5Sr 0.5) 0.9La 0.1Co 0.8Fe 0.2O 3-δCoprecipitation synthetic
With 5.880g Ba (NO 3) 2(analyzing pure), 4.761g Sr (NO 3) 2(analyzing pure), 14.117g Co (NO 3) 36H 2O (analyzing pure), 2.165g La (NO 3) 36H 2O (analyzing pure) and 4.038g Fe (NO 3) 39H 2O (analyzing pure) wiring solution-forming, and this solution is added drop-wise to lentamente the excessive N aHCO that is stirring 3In the aqueous solution, adjusting the pH value simultaneously is between 7～9, stirs 4h again.Wash and suction filtration with distilled water through five times then, to guarantee to remove sodium ion and unnecessary nitrate ion, after the alcohol washing is removed moisture 3 times.In 120 ℃ of baking ovens, dry 12h, obtain presoma.Presoma at 1000 ℃ of calcining 5h, is obtained (the Ba of cubic perovskite structure 0.5Sr 0.5) 0.9La 0.1Co 0.8Fe 0.2O 3-δ
Embodiment 5:0.05mol (Ba 0.5Sr 0.5) 0.9La 0.1Co 0.8Fe 0.2O 3-δSol-gel process synthetic
With 5.880g Ba (NO 3) 2(analyzing pure), 4.761g Sr (NO 3) 2(analyzing pure), 14.117g Co (NO 3) 36H 2O (analyzing pure), 4.038g Fe (NO 3) 39H 2O (analyzing pure) and 2.165g La (NO 3) 36H 2O (analyzing pure) presses chemical formula element ratio wiring solution-forming, and then in the metal ion: ethylenediamine tetra-acetic acid (EDTA): the ratio of citric acid=1: 1: 2 takes by weighing 29.22g EDTA and 42.028g citric acid.EDTA joined in the 50ml ammonia spirit and stir pour in the nitrate solution for preparing after making it to dissolve fully, add citric acid then and regulate pH value to 7 with ammoniacal liquor, add thermal agitation and form transparent colloidal sol, further colloidal sol is obtained presoma 250 ℃ of processing, at last presoma is promptly obtained (the Ba of cubic perovskite structure at 1000 ℃ of roasting 5h 0.5Sr 0.5) 0.9La 0.1Co 0.8Fe 0.2O 3-δ

Claims (3)

1. an intermediate temperature solid oxide fuel cell cathode material is characterized in that, its composition general formula is (Ba 0.5Sr 0.5) 1-XLa xCo 0.8Fe 0.2O 3-δ, 0.05≤x≤0.15.
2. according to right 1 described cathode material for solid-oxide fuel cell, it is characterized in that when x=0.05, the structural formula of described cathode material for solid-oxide fuel cell is (Ba 0.5Sr 0.5) 0.95La 0.05Co 0.8Fe 0.2O 3-δ
3. according to right 1 described cathode material for solid-oxide fuel cell, it is characterized in that when x=0.15 that the structural formula of described cathode material for solid-oxide fuel cell is (Ba 0.5Sr 0.5) 0.85La 0.15Co 0.8Fe 0.2O 3-δ
CNA2008100557471A 2008-01-08 2008-01-08 Medium-low temperature solid-oxide fuel battery cathode material Pending CN101222060A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102738492A (en) * 2011-03-31 2012-10-17 三星电子株式会社 Material for solid oxide fuel cell, cathode including the material, and solid oxide fuel cell including the same
CN103367767A (en) * 2013-07-12 2013-10-23 黑龙江大学 Moderate-temperature solid oxide fuel battery doped double-perovskit-structure cathode material and preparation method thereof
EP2538474A3 (en) * 2011-06-21 2014-12-17 Samsung Electro-Mechanics Co., Ltd Material for solid oxide fuel cell, cathode including the material, and solid oxide fuel cell including the material
CN109244536A (en) * 2018-09-21 2019-01-18 佛山皖和新能源科技有限公司 A kind of preparation method of densification isotypy composite solid electrolyte material
CN113574705A (en) * 2019-03-19 2021-10-29 堺化学工业株式会社 Powder for air electrode of solid oxide fuel cell and method for producing same
CN113964331A (en) * 2021-10-26 2022-01-21 山东科技大学 Strontium-cobalt-based perovskite composite cathode with multi-stage structure and preparation method thereof

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102738492A (en) * 2011-03-31 2012-10-17 三星电子株式会社 Material for solid oxide fuel cell, cathode including the material, and solid oxide fuel cell including the same
EP2506351A3 (en) * 2011-03-31 2014-11-12 Samsung Electro-Mechanics Co., Ltd Material for solid oxide fuel cell, cathode including the material, and solid oxide fuel cell including the same
EP2538474A3 (en) * 2011-06-21 2014-12-17 Samsung Electro-Mechanics Co., Ltd Material for solid oxide fuel cell, cathode including the material, and solid oxide fuel cell including the material
CN103367767A (en) * 2013-07-12 2013-10-23 黑龙江大学 Moderate-temperature solid oxide fuel battery doped double-perovskit-structure cathode material and preparation method thereof
CN103367767B (en) * 2013-07-12 2015-12-09 黑龙江大学 A kind of application of intermediate temperature solid oxide fuel cell doping structure of double perovskite cathode material
CN109244536A (en) * 2018-09-21 2019-01-18 佛山皖和新能源科技有限公司 A kind of preparation method of densification isotypy composite solid electrolyte material
CN109244536B (en) * 2018-09-21 2020-04-24 深圳凯泽鑫电子有限公司 Preparation method of compact and uniform solid composite electrolyte material
CN113574705A (en) * 2019-03-19 2021-10-29 堺化学工业株式会社 Powder for air electrode of solid oxide fuel cell and method for producing same
CN113964331A (en) * 2021-10-26 2022-01-21 山东科技大学 Strontium-cobalt-based perovskite composite cathode with multi-stage structure and preparation method thereof

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