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A-site Ba, Sr, Ca ions-doped SrCo0.8Fe0.2O3-delta-base perovskite oxygen permeable membrane material and application thereof

An oxygen-permeable membrane and perovskite technology, which is applied in the field of inorganic oxygen-permeable membrane materials, can solve the problems of difficulty in forming a pure-phase perovskite structure, small bond energy, and difficulty in synthesizing oxygen-permeable membrane materials

Inactive Publication Date: 2011-01-19
LIAONING UNIVERSITY OF PETROLEUM AND CHEMICAL TECHNOLOGY
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Problems solved by technology

For SrCo 0.8 Fe 0.2 o 3-δ Perovskite matrix materials, from the perspective of ion valence, Ba, Sr and Ca are the three best candidate ions for A-site doping, but it is difficult to dope Ca ions in the perovskite oxygen-permeable film. Because the ionic radius of Ca is smaller than that of Ba and Sr, Ca ions must be matched with La or Ba with larger ionic radii to synthesize pure-phase perovskite materials, but due to the large gap between the radii of La or Ba ions and Ca ions , Doping more Ca ions in the material is often difficult to form a pure-phase perovskite structure, which limits the doping ratio of Ca in the A site of the perovskite material (often less than 10%)
Ca is a relatively cheap element, and the bond energy of the Ca-O bond is small. From these two factors, doping Ca is more beneficial to reduce the cost of the oxygen permeable film and increase the oxygen permeability. However, in perovskite materials Oxygen permeable membrane materials whose A-site Ca ion ratio exceeds 10% are difficult to synthesize

Method used

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  • A-site Ba, Sr, Ca ions-doped SrCo0.8Fe0.2O3-delta-base perovskite oxygen permeable membrane material and application thereof
  • A-site Ba, Sr, Ca ions-doped SrCo0.8Fe0.2O3-delta-base perovskite oxygen permeable membrane material and application thereof
  • A-site Ba, Sr, Ca ions-doped SrCo0.8Fe0.2O3-delta-base perovskite oxygen permeable membrane material and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] (I) Ba 0.33 Sr 0.33 Ca 0.34 co 0.8 Fe 0.2 o 3-δ solid phase synthesis

[0028] Weigh the stoichiometric Ba(NO 3 ) 2 , Sr(NO 3 ) 2 , CaCO 3 、Co 3 o 4 , Fe 2 o 3 , according to Ba 0.33 Sr 0.33 Ca 0.34 co 0.8 Fe 0.2 o 3-δ The ratio of the elements to configure the mixture powder, using ethanol as the medium, ball milling in a steel ball mill tank for 5 hours, after mixing evenly, drying in an oven, and then roasting in a muffle furnace at 950 ° C for 5 hours, and then the obtained powder The body was put back into a steel ball mill jar for ball milling for 5 hours, and then roasted, and the ball milling and roasting processes were carried out three times. Then get Ba 0.33 Sr 0.33 Ca 0.34 co 0.8 Fe 0.2 o 3-δ The oxygen-permeable membrane powder is pressed into an oxygen-permeable membrane with a stainless steel mold, and the oxygen-permeable membrane is fired at 1100°C for 5 hours to obtain the required oxygen-permeable membrane.

Embodiment 2

[0030] (II) Ba 0.33 Sr 0.33 Ca 0.34 co 0.8 Fe 0.2 o 3-δ EDTA-citric acid synthesis method

[0031] First, a known concentration of Ba(NO 3 ) 2 Solution is poured in the prepared 2000ml beaker, then add the EDTA acid and ammonia solution of metering ratio, fully stir, make Ba(NO 3 ) 2 Complete dissolution gave a clear solution. Take appropriate amount of CaCO 3 , dissolved with nitric acid to obtain a clear solution with Ba(NO 3 ) 2 The solutions were mixed, and then a proper amount of Sr(NO 3 ) 2 , Co(NO 3 ) 2 , Fe(NO 3 ) 3 The solution is added to the clarified solution prepared above, and the configuration ratio of various metal ions is Ba 0.33 Sr 0.33 Ca 0.34 co 0.8 Fe 0.2 o 3-δ . After the mixed solution of the metal ions used was stirred for a few minutes, an appropriate amount of citric acid and EDTA acid was added to the solution. In the experiment, the ratio of EDTA acid:total amount of metal ions:substance amount of citric acid was 1:1:1.5. T...

Embodiment 3

[0033] (III)Ba 0.4 Sr 0.4 Ca 0.2 co 0.8 Fe 0.2 o 3-δ solid phase synthesis

[0034] Weigh the stoichiometric Ba(NO 3 ) 2 , Sr(NO 3 ) 2 , CaCO 3 、Co 3 o 4 , Fe 2 o 3 , according to Ba 0.4 Sr 0.4 Ca 0.2 co 0.8 Fe 0.2 o 3-δ The ratio of the elements to configure the compound compound, using ethanol as the medium, milling in a steel ball mill tank for 5 hours, after mixing, drying in an oven, and then roasting in a muffle furnace at 950 ° C for 5 hours, and then the obtained powder The body was put back into a steel ball mill jar for ball milling for 5 hours, and then roasted, and the ball milling and roasting processes were carried out three times. Then get Ba 0.33 Sr 0.33 Ca 0.34 co 0.8 Fe 0.2 o 3-δ The oxygen-permeable membrane powder is pressed into an oxygen-permeable membrane with a stainless steel mold, and the oxygen-permeable membrane is fired at 1100°C for 5 hours to obtain the required oxygen-permeable membrane.

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Abstract

The invention provides an A-site Ba, Sr, Ca ions-doped SrCo0.8Fe0.2O3-delta-base perovskite oxygen permeable membrane material and application thereof, and relates to inorganic oxygen permeable membrane material, wherein, Ba, Sr and Ca elements are doped to the A-site of SrCo0.8Fe0.2O3-delta at the same time. The general formula of the material is BaxSr1-x-yCayCo0.8Fe0.2O3-delta, wherein, x is 0.1-0.9, and y is 0.1-0.9. In the invention, by adjusting the doping ratio of the three metal ions, the material forms a cubic perovskite structure; and studies show that the melting point of the material is lower than that of an A-site single-ion or dual-ion-doped perovskite material, and the material has stable structure and higher oxygen permeation quantity, thus being applicable to the fields such as oxygen permeable membrane sealing, pure oxygen separation, partial oxidation of methane, a solid oxide fuel cell cathode material and the like.

Description

technical field [0001] The invention belongs to an inorganic oxygen-permeable membrane material, in particular to a SrCo doped with Ba, Sr, and Ca triple ions at the A site 0.8 Fe 0.2 o 3-δ Perovskite-based oxygen-permeable membrane materials and their applications. Background technique [0002] Perovskite ceramic oxygen permeable membrane material refers to a new type of ceramic membrane with both oxygen ion conductivity and electronic conductivity. At high temperature (especially when the temperature is greater than 600°C), when there is an oxygen concentration gradient on both sides of the membrane, oxygen will be conducted in the form of oxygen ions through the bulk phase from the high oxygen pressure region to the low oxygen pressure region, and at the same time, the electrons will Conduction in the opposite direction keeps the material electrically neutral. This material does not require an external circuit to conduct electrons like solid oxide fuel cells, and beca...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C04B35/32
Inventor 李其明连丕勇李芳
Owner LIAONING UNIVERSITY OF PETROLEUM AND CHEMICAL TECHNOLOGY
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