CN1864830A - A biphase mixed conducting oxygen-permeable membrane and preparation method thereof - Google Patents
A biphase mixed conducting oxygen-permeable membrane and preparation method thereof Download PDFInfo
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Abstract
The invention relates to biphasic mixed conduct oxygen permeable membrane and the method for preparing the same. It comprises electronic conductive phase prepared with soild phase reaction synthetic method and oxygen-ion conductive phase got by means of oxalate coprecipitation. It is characterized in that the method comprises following steps: mixing perovskite oxide of electronic conductive phase with fluotite metallic oxide of oxygen-ion conductive phase according to volume proportion of 0.667-1.5: 1; pressing blank; calcinating under 1500-1600 Deg. C; the electronic conductive phase and oxygen-ion conductive phase in got oxygen-permeable membrane interleave with each other and forms continous passage respectively; the molecular formula of perovskite oxide and fluotite metallic oxide are: La1-xAxCrO3-deltaand Ce1-yRyO2-z, A is Ca or Sr, R is Sm, Gd or Y or combination of them, 0<x<=0.4, 0<y<=0.4. <0=The oxygen-permeable membrane is characterized by high oxygen-permeability, chemical stability and mechanical stability, it is stable under air and reductive atmosphere and under temperature below 1000 Deg .C. it can be usd as electrode material for oxygen segregator, membrane reactor and fuel battery.
Description
Technical field:
The invention belongs to compact ceramic oxygen permeable membrane material applied technical field, particularly oxonium ion-electronics biphase mixed conducting oxygen-permeable membrane.
Background technology:
Composite conductor oxygen-permeating film can be isolated pure oxygen owing to have oxygen-ion conduction and electronic conductance simultaneously from oxygen-containing gas.For example a kind of composite conductor oxygen-permeating film material La with single perovskite phase structure has been reported in Japan " chemical communication " (Chem.Lett.1743-1746,2000)
1-xSr
xCo
1-yFe
yO
3-δWherein oxonium ion and electronics all this single perovskite mutually in conduction, its oxygen vacancy concentration height, oxonium ion and electronic conduction ability are strong, therefore the oxygen permeability of this type of material is higher, but because its thermal coefficient of expansion is bigger, cobalt and iron in the lattice easily are reduced, the stability of material and bad mechanical property can't be applicable to reducing atmosphere and long-term high-temperature operation.Another kind of composite conductor oxygen-permeating film is that wherein oxonium ion and electronics conduct in passage separately respectively by the compound mixed conductor of two-phase of oxide ion conduction phase and electronic conduction phase composition.For example European patent EP 0399833A1 has disclosed a kind of biphase mixed conducting oxygen-permeable membrane, wherein oxide ion conduction is the zirconia of stabilisation mutually, electronic conduction is platinum or other noble metal mutually, but because the zirconic oxygen ionic conductivity of stabilisation is lower, the oxygen flow ability of material is lower.United States Patent (USP) 5,478 has disclosed with Bi in 444
2O
3-δBase oxide is the two-phase oxygen permeable film material of oxide ion conduction phase, because Bi
2O
3-δAt high temperature easily be reduced, its chemical stability is relatively poor.U.S.'s " electrochemistry magazine " (J.Electrochem.Soc., 147,2814-2821,2000) has reported a kind of two-phase oxygen permeable film material, and wherein oxide ion conduction is Ce mutually
0.8Gd
0.2O
2-δ, electronic conduction is perovskite oxide La mutually
0.7Sr
0.3MnO
3-δ, but owing to exist reaction between this two-phase, the oxygen flow ability of material descends along with the prolongation of time, stability is not enough.Chinese patent 02124417.0 has disclosed a kind of oxide ion conduction is perovskite mutually mutually with electronic conduction two-phase oxygen permeation membrane, wherein electronic conduction phase Ba
1-xSr
xCo
1-yFe
yO
3-δResemble a continuous lead through oxide ion conduction phase La
1-x 'Sr
X 'Ga
1-y 'Fe
Y 'O
3-δIn the diaphragm skeleton that constitutes, though this material oxygen transmission rate is higher, because mixed conductor Ba
1-xSr
xCo
1-yFe
yO
3-δExistence make that its anti-reducing power is relatively poor.
Holland has reported La in " solid-state ionics " (Solid State Ionics, 171,1-15,2004)
1-xA
xCrO
3-δ(A=Ca, Sr) system can stable existence in reducing atmosphere and is at high temperature had high electronic conductivity, can be with the metallic interconnect materials that is SOFC; Holland " solid-state ionics " (Solid State Ionics, 96,83-88,1997) report La
1-xA
xCrO
3-δThe oxygen ionic conductivity of (A=Ca, Sr) system has only 10 at 1000 ℃
-6～10
-5S/cm, so this system is not mixed conductor, itself do not have the oxygen flow ability; Holland " solid-state ionics " (Solid State Ionics, 83,1-16,1996) and Holland " electrochemistry communication " (Electrochemistry Communications, 6,743-746,2004) report Ce
1-yR
yO
2-z(R is one or more among Sm, Gd, the Y) system is a kind of good pure oxygen ion conductor, and oxygen ionic conductivity has surpassed 0.1S/cm in the time of 900 ℃
-1High nearly order of magnitude of the zirconia (YSZ) of the oxygen ion conductor stabilized with yttrium oxide that ratio is commonly used, but its electronic conductivity is very little, than little two orders of magnitude of oxygen ionic conductivity, therefore this system neither mixed conductor, itself does not have the oxygen flow ability.So far yet there are no La
1-xA
xCrO
3-δ(A=Ca, Sr) system and Ce
1-yR
yO
2-zSystem is formed the report of two-phase oxygen permeable membrane.
Summary of the invention:
The present invention proposes a kind of biphase mixed conducting oxygen-permeable membrane with high oxygen transmission rate and high stability and preparation method thereof.
Biphase mixed conducting oxygen-permeable membrane of the present invention by electronic conduction phase and oxide ion conduction phase composition, is characterized in that electronic conduction is perovskite oxide mutually, and oxide ion conduction is the fluorite type metal oxide mutually; Electronic conduction is interweaved, twines the also passage of the continuous conducting of each self-forming mutually mutually with oxide ion conduction; Electronic conduction is 0.67～1.5: 1 with oxide ion conduction volume ratio mutually; The molecular formula of described perovskite oxide and fluorite type metal oxide is respectively La
1-xA
xCrO
3-δAnd Ce
1-yR
yO
2-z, wherein A is Ca or Sr, R is one or more among Sm, Gd, the Y, and 0＜x≤0.4,0＜y≤0.4, z=y/2, δ are the non-stoichiometry of oxygen, scope is 0＜δ＜0.3.
The preparation method of biphase mixed conducting oxygen-permeable membrane of the present invention, earlier prepare the electronic conduction phase with synthesis by solid state reaction, that is: take by weighing after raw material mixes according to the metering ratio of molecular formula, at 1250 ℃～1350 ℃ roastings and ball milling to obtain the electronic conduction phase of pure phase; Make the oxide ion conduction phase with oxalate coprecipitation method, that is: take by weighing raw material according to the metering ratio of molecular formula and be made into mixed solution, join in the oxalate solution, the pH value of regulator solution makes it keep neutral, and constantly stirs; 700～900 ℃ of roastings that are deposited in that obtain promptly obtained the oxide ion conduction phase in 2～10 hours; It is characterized in that described electronic conduction is perovskite oxide mutually, described oxide ion conduction is the fluorite type metal oxide mutually; The molecular formula of described perovskite oxide and fluorite type metal oxide is respectively La
1-xA
xCrO
3-δAnd Ce
1-yR
yO
2-z, wherein A is Ca or Sr, R is one or more among Sm, Gd, the Y, and 0＜x≤0.4,0＜y≤0.4, z=y/2, δ are the non-stoichiometry of oxygen, scope is 0＜δ＜0.3; With the above-mentioned electronic conduction for preparing mutually with oxide ion conduction mutually by volume 0.67～1.5: 1 ratio mix, under the pressure of 200～450 MPas, be pressed into the ceramic body of required form, carry out densified sintering product at 1500 ℃～1600 ℃ again.
Compared with prior art, biphase mixed conducting oxygen-permeable membrane of the present invention is because the electronic conduction that adopts is the perovskite oxide La that chemical stability is good, electronic conductivity is high mutually
1-xA
xCrO
3-δ(A=Ca, Sr), oxide ion conduction be the outstanding and good fluorite oxide Ce of chemical stability for oxygen ionic conductivity mutually
1-yRyO
2-z(R is one or more among Sm, Gd, the Y), these two kinds of oxides compatible good, can not produce chemical reaction, two-phase is evenly distributed and is interweaved, twines and the passage of the continuous conducting of each self-forming, the thermal coefficient of expansion of two-phase is close, therefore at high temperature oxonium ion and electronic conductivity all than higher, also make material have better chemical stability and mechanical stability, can and keep high oxygen permeability in the medium-term and long-term existence of strongly reducing atmosphere.For example the oxygen permeability of the tubular film of 1.1 millimeters thick under 950 ℃ and air/carbon monoxide gradient reached 1.25ml.cm
-2.min
-1, and the fracture phenomena of performance decrease or film pipe does not appear in the long-time operation process.The present invention has overcome the shortcoming that existing composite conductor oxygen-permeating film can't have both high chemical stability and high oxygen flow ability.In addition, compare as electronic conduction two-phase mixed conductor mutually with the existing noble metal that adopts, the present invention adopts the perovskite oxide La of relatively easy acquisition
1-xA
xCrO
3-δ(A=Ca, Sr), more favourable from the consideration of cost.Biphase mixed conducting oxygen-permeable membrane of the present invention can be used for selecting oxygen separation from contain oxygen gas mixture, is used to construct membrane reactor and carries out the technology that partial oxidation of methane is equipped with synthesis gas, also can be used for the electrode material of SOFC.
Description of drawings:
Fig. 1 is 0.67: 1 La for volume ratio
0.8Sr
0.2CrO
3-δ-Ce
0.8Sm
0.2O
1.9(LSC/CSO) X-ray diffraction of two-phase oxygen permeation membrane (XRD) spectrogram;
Fig. 2 is Electronic Speculum (SEM) photo that LSC/CSO obtains with backscattered electron;
Fig. 3 is that the oxygen permeating amount of LSC/CSO laminar film in air/helium atmosphere of 0.67: 1 and 1.0 millimeters thick is with the variation of temperature curve for volume ratio;
Fig. 4 is that the oxygen permeating amount of LSC/CSO two-phase oxygen permeation membrane in air/helium atmosphere of 1: 1 and 0.6 millimeters thick is with the variation of temperature curve for volume ratio;
Fig. 5 is that the oxygen permeating amount of LSC/CSO tubular film in air/CO atmosphere of 0.67: 1 and 1.1 millimeters thick is with the variation of temperature curve for volume ratio;
Fig. 6 is LSC/CSO tubular film oxygen permeating amount curve over time under 950 ℃ in air/CO atmosphere.
The specific embodiment:
Below be embodiments of the invention.
Embodiment 1: preparation LSC/CSO sheet two-phase oxygen permeation membrane
Used Ca-Ti ore type La in the present embodiment
0.8Sr
0.2CrO
3-δ(LSC) powder adopts conventional solid reaction process synthetic: accurately take by weighing 14.762 gram SrCO
3(analyzing pure), 65.160 gram La
2O
3(＞99.99%) and 37.998 gram Cr
2O
3(analyzing pure) powder mixes back ball milling 20 hours in ethanol; 1300 ℃ of roastings 10 hours, ball milling was 20 hours after the roasting, repeated 2 times, and the LSC powder of acquisition detects with X-ray diffraction (XRD) and is the pure phase perovskite.
Used fluorite type Ce in the present embodiment
0.8Sm
0.2O
1.9(CSO) powder obtains with oxalate coprecipitation method: accurately take by weighing 43.590 gram Sm
2O
3(＞99.99%) is dissolved in the salpeter solution and is made into Sm
3+Ion concentration is the solution of 1 mol, takes by weighing 108.529 gram Ce (NO
3)
36H
2O (analyzing pure) is dissolved in the deionized water and is made into Ce
3+Ion concentration is the solution of 1 mol, pipette these two kinds of solution and evenly mixing by 1: 4 volume ratio, then the speed of mixed solution with 10 ml/min is added drop-wise in the oxalic acid solution of 0.1 mol, the pH value with the ammoniacal liquor regulator solution makes it keep neutral simultaneously, and constantly stirs; The precipitation that obtains is spent ionized water and ethanol cleaning respectively, after 50 ℃ of oven dry, promptly obtained the CSO powder in 2 hours 800 ℃ of roastings.Detecting with XRD is the pure phase fluorite structure.
Took by weighing 7.171 gram LSC and 12.074 gram CSO powders in 0.67: 1 by volume respectively, grinding in mortar mixes powder, make the flaky pottery base substrate with isostatic pressing method at the forming under the pressure of 300 MPas, reduce to room temperature at 1550 ℃ of sintering after 10 hours, promptly get sheet two-phase LSC/CSO composite conductor oxygen-permeating film.
Detect the phase composition of LSC/CSO two-phase film by XRD.This two-phase film only contains the diffraction maximum of the CSO of the LSC of perovskite structure and fluorite structure as can be seen from XRD spectra Fig. 1 of two-phase oxygen permeation membrane LSC/CSO, impurity peaks do not occur, shows between the two-phase not react.From the SEM photo Fig. 2 on LSC/CSO two-phase film surface, can be clear that, diaphragm mainly is made of two-phase, two-phase is evenly distributed and is interweaved, and the pattern of diaphragm section is similar to accompanying drawing 2, can judge that in conjunction with morphology observation two-phase passage separately is to twine mutually.For determining the concrete ownership of two-phase, analyze with energy dispersive X-ray spectrum (EDX) instrument, among the discovery figure brighter one corresponding be CSO oxide ion conduction phase, and darker one be LSC electronic conduction phase mutually.With the AC impedance spectrometer total conductivity of two-phase film is measured, total conductivity has surpassed 1S/cm in the time of 900 ℃
-1, oxygen ionic conductivity in the pure CSO illustrates that electronic conduction is continuous conducting mutually.
The LSC/CSO sheet sample that with thickness is 1.0mm is connected on the alundum tube 1000 ℃ of lower seals with the glass sealing agent, and a side of film is exposed in the flow air, and opposite side then is exposed in high-purity helium that flow is fixed on 30ml/min.From air, be penetrated into the concentration gas chromatographic analysis of the oxygen in the helium by the two-phase film.Oxygen permeability is seen accompanying drawing 3 with the relation of temperature.The experimental temperature scope is 750～1000 ℃, and temperature raises, and partial pressure of oxygen and oxygen permeability in the helium all increase, respectively 2.0 * 10
-4～5.4 * 10
-3Atm and 0.0070～0.20ml.cm
-2.min
-1Change in the scope, in the time of 950 ℃, oxygen permeating amount is 0.14ml.cm
-2.min
-1, this numerical value shows that oxide ion conduction mutually also is continuous conducting.The oxygen infiltration cooled to room temperature behind the oxygen permeability test through 320 hours laminar film is still excellent, illustrates that the mechanical stability of LSC/CSO is better.
Embodiment 2: the LSC/CSO sheet two-phase oxygen permeation membrane for preparing other volume ratio
The volume ratio of LSC and CSO powder changes 1: 1 respectively into and 1.5: 1 when preparing LSC/CSO two-phase film by LSC powder and CSO powder among the embodiment 1, the pressure of isostatic pressing method moulding makes 200 MPas and 450 MPas respectively into, sintering temperature makes 1600 ℃ and 1500 ℃ respectively into, other condition is constant, also make with embodiment 1 in the kin two-phase oxygen permeation membrane of sheet LSC/CSO biphase mixed conducting oxygen-permeable membrane.As volume ratio is that the oxygen permeating amount of LSC/CSO sheet two-phase oxygen permeation membrane in air/helium atmosphere of 1: 1 and 0.6 millimeters thick is shown in Figure 4 with the variation of temperature curve, and the excursion of oxygen permeability between 775～1000 ℃ is 0.018～0.22ml.cm
-2.min
-1, this shows that also the two-phase in the two-phase film is respectively continuous conducting because oxide ion conduction mutually any one mutually discontinuous conducting all can cause sample not have the oxygen flow ability with electronic conductance mutually.
Embodiment 3: the sheet two-phase oxygen permeation membrane for preparing other composition
Adjusting ratio raw materials used in embodiment 1 solid reaction process and changing sintering temperature is 1350 ℃, and other condition is constant, is prepared into pure phase perovskite La
0.95Sr
0.05CrO
3-δAnd La
0.6Sr
0.4CrO
3-δPowder.
With raw materials used SrCO in embodiment 1 solid reaction process
3Change CaCO into
3, changing sintering temperature is 1250 ℃, and other condition is constant, and being prepared into Ca content is x=0.05,0.25 and 0.4 pure phase perovskite La
1-xCa
xCrO
3-δPowder.
Adjust to pipette in embodiment 1 oxalate coprecipitation method and contain Sm
3+Solution and contain Ce
3+The volume ratio of solution, other condition is constant, is prepared into the Ce of pure phase fluorite structure
0.9Sm
0.1O
1.95And Ce
0.6Sm
0.4O
1.8
With raw materials used Sm in embodiment 1 oxalate coprecipitation method
2O
3The all or part of Gd that changes into
2O
3, under conditions of similarity, be prepared into the Ce of the pure phase fluorite structure that consists of x=0.05 and y=1, x=0.2 and y=1, x=0.4 and y=1, x=0.2 and y=0.5 respectively
1-x(Sm
1-yGd
y)
xO
2-z
With raw materials used Sm in embodiment 1 oxalate coprecipitation method
2O
3The all or part of Y that changes into
2O
3, under conditions of similarity, be prepared into the Ce of the pure phase fluorite structure that consists of x=0.1 and y=1, x=0.25 and y=1, x=0.4 and y=1, x=0.1 and y=0.2, x=0.3 and y=0.8 respectively
1-x(Sm
1-yY
y)
xO
2-z
With raw materials used Sm in embodiment 1 oxalate coprecipitation method
2O
3All change the Gd that mol ratio wherein is respectively 1: 1,1: 3 and 3: 1 into
2O
3And Y
2O
3Mixture, under conditions of similarity, be prepared into the Ce of the pure phase fluorite structure that consists of x=0.1 and y=0.5, x=0.25 and y=0.25, x=0.4 and y=0.75 respectively
1-x(Gd
1-yY
y)
xO
2-z
With raw materials used Sm in embodiment 1 oxalate coprecipitation method
2O
3Part changes wherein Gd into
2O
3And Y
2O
3Mol ratio is respectively the mixture of 1: 1,1: 3 and 3: 1, is prepared into respectively under conditions of similarity and consists of x=0.1, y=0.2 and z=0.2, x=0.25, y=0.1 and z=0.3, x=0.4, the Ce of the pure phase fluorite structure of y=0.6 and z=0.2
1-x(Sm
1-y-zGd
yY
z)
xO
2-z '
Electronic conduction phase La with above-mentioned preparation
0.95Sr
0.05CrO
3-δ, La
0.6Sr
0.4CrO
3-δPowder and the oxide ion conduction of above-mentioned preparation Ce mutually
0.6Sm
0.4O
1.8, Ce
1-x(Sm
1-yGd
y)
xO
2-zAnd Ce
1-x(Sm
1-y-zGd
yY
z)
xO
2-z '0.67: 1 by volume requirement of powder mix, it is constant to prepare other condition of LSC/CSO two-phase film by LSC powder and CSO powder among the embodiment 1, also makes and the similar two-phase oxygen permeation membrane of LSC/CSO two-phase oxygen permeation membrane.
Electronic conduction phase La with above-mentioned preparation
1-xCa
xCrO
3-δPowder and the oxide ion conduction of above-mentioned preparation Ce mutually
0.9Sm
0.1O
1.95, Ce
1-x(Sm
1-yY
y)
xO
2-zAnd Ce
1-x(Gd
1-yY
y)
xO
2-z1.5: 1 by volume requirement of powder mix, it is constant to prepare other condition of LSC/CSO two-phase film by LSC powder and CSO powder among the embodiment 1, also makes and the kin two-phase oxygen permeation membrane of above-mentioned LSC/CSO two-phase oxygen permeation membrane.
Embodiment 4: preparation LSC/CSO tubulose two-phase oxygen permeation membrane
The LSC powder and the CSO powder of preparation among the embodiment 1 were taken by weighing 21.513g and 36.222g in 0.67: 1 by volume respectively, ball milling mixed powder in 24 hours in the alcohol medium, under the pressure of 350 MPas, make the tubular ceramic base substrate with isostatic pressing method, carried out being cooled to room temperature behind the sintering in 10 hours 1550 ℃ of insulations, promptly get thick 1.1 millimeters tubulose biphase mixed conducting oxygen-permeable membrane.
The two ends of this LSC/CSO tubular film are connected on the alundum tube 1000 ℃ of lower seals with the glass sealing agent, and a side of film is exposed in the air, and opposite side then is exposed in the CO gas that flow is fixed on 30ml/min.Oxygen is penetrated into the CO side through the film pipe from air, promptly generate CO with the CO reaction
2, wherein CO and CO
2The concentration gas chromatographic analysis, the infiltration capacity of oxygen is by CO and CO
2Between chemical reaction equilibrium calculate.The experimental temperature scope is 800～1000 ℃, and temperature raises, CO and CO
2Concentration ratio diminish CO/CO
2The partial pressure of oxygen of gaseous mixture increases, and partial pressure of oxygen is 5.8 * 10
-19～1.2 * 10
-14Change between the atm, wanting among the partial pressure of oxygen gradient ratio embodiment 1 of generation is big by 10
11～10
15Doubly; Shown in Figure 5 with the variation of temperature curve as the oxygen permeating amount of LSC/CSO in air/CO atmosphere, oxygen permeability also raises with temperature and increases, and excursion is 0.51-1.58ml.cm
-2.min
-1, oxygen permeating amount has reached 1.25ml.cm in the time of 950 ℃
-2.min
-1, than the big nearly order of magnitude of the oxygen permeating amount that under air/helium gradient, obtains among the embodiment 1.
Comparative example 1: the stability of composite conductor oxygen-permeating film
As the LSC/CSO tubular film in air/CO atmosphere oxygen permeating amount curve is shown in Figure 6 over time under 950 ℃, be 0.21atm/1.2 * 10 950 ℃ and partial pressure of oxygen gradient
-15Under the condition of atm, the oxygen permeating amount of the LSC/CSO two-phase tubular film of preparation maintains 1.2～1.3ml.cm always among the embodiment 4 in 110 hours measuring process
-2.min
-1Between, do not see the decline of its oxygen permeability and the damage phenomenon of breaking of film body in the experimentation that under air/CO gradient, continues 800 hours in addition.And the La that in U.S.'s " electrochemistry magazine " (J.Electrochem.Soc., 147,2814-2821,2000), reports
0.7Sr
0.3MnO
3-δ-Ce
0.8Gd
0.2O
2-δThe two-phase oxygen permeation membrane is because electronic conduction phase La
0.7Sr
0.3MNO
3-δChemism higher with oxide ion conduction Ce mutually
0.8Gd
0.2O
2-δBetween exist reaction, 950 ℃ and less partial pressure of oxygen gradient (air/helium) down the oxygen flow ability of oxygen permeation membrane promptly descend along with the prolongation of time, stability is not enough.In 800～900 ℃ of temperature ranges, the composite conductor oxygen-permeating film material that has the maximum oxygen penetrating power is the SrCo with single perovskite phase structure of report in Japan " chemical communication " (Chem.Lett., 1743-1746,1985) in currently reported
0.8Fe
0.2O
3-δ, its oxygen permeability can reach 2ml.cm under 850 ℃ and air/helium gradient
-2.min
-1Above numerical value; But Holland " catalysis communication " (Catal.Lett.30,201-212,1995) oxygen permeation membrane that constitutes by this kind material of report in reducing atmosphere, decompose rapidly and under big partial pressure of oxygen gradient film body produce soon and break, this be because contain that oxygen room that the Co/Fe atom that easily is reduced causes existing in materials chemistry less stable and the material bodies high concentration causes that its thermal coefficient of expansion is big, the crystal lattice stress of material internal big due to.
Claims (2)
1, a kind of biphase mixed conducting oxygen-permeable membrane by electronic conduction phase and oxide ion conduction phase composition, is characterized in that electronic conduction is perovskite oxide mutually, and oxide ion conduction is the fluorite type metal oxide mutually; Electronic conduction is interweaved, twines the also passage of the continuous conducting of each self-forming mutually mutually with oxide ion conduction; Electronic conduction is 0.67～1.5: 1 with oxide ion conduction volume ratio mutually; The molecular formula of described perovskite oxide and fluorite type metal oxide is respectively La
1-xA
xCrO
3-δAnd Ce
1-yR
yO
2-z, wherein A is Ca or Sr, R is one or more among Sm, Gd, the Y, and 0＜x≤0.4,0＜y≤0.4, z=y/2, δ are the non-stoichiometry of oxygen, scope is 0＜δ＜0.3.
2, the preparation method of the described biphase mixed conducting oxygen-permeable membrane of claim 1, earlier prepare the electronic conduction phase with synthesis by solid state reaction, that is: take by weighing after raw material mixes according to the metering ratio of molecular formula, at 1250 ℃～1350 ℃ roastings and ball milling to obtain the electronic conduction phase of pure phase; Make the oxide ion conduction phase with oxalate coprecipitation method, that is: take by weighing raw material according to the metering ratio of molecular formula and be made into mixed solution, join in the oxalate solution, the pH value of regulator solution makes it keep neutral, and constantly stirs; 700～900 ℃ of roastings that are deposited in that obtain promptly obtained the oxide ion conduction phase in 2～10 hours; It is characterized in that described electronic conduction is perovskite oxide mutually, described oxide ion conduction is the fluorite type metal oxide mutually; The molecular formula of described perovskite oxide and fluorite type metal oxide is respectively La
1-xA
xCrO
3-δAnd Ce
1-yR
yO
2-z, wherein A is Ca or Sr, R is one or more among Sm, Gd, the Y, and 0＜x≤0.4,0＜y≤0.4, z=y/2, δ are the non-stoichiometry of oxygen, scope is 0＜δ＜0.3; With the above-mentioned electronic conduction for preparing mutually with oxide ion conduction mutually by volume 0.67～1.5: 1 ratio mix, under the pressure of 200～450 MPas, be pressed into the ceramic body of required form, carry out densified sintering product at 1500 ℃～1600 ℃ again.
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| US20110176980A1 (en) * | 2007-08-31 | 2011-07-21 | Technical University Of Denmark | Membrane with a stable nanosized microstructure and method for producing same |
| CN101306330B (en) * | 2008-02-01 | 2011-11-02 | 中国科学技术大学 | Production method of mixed conductor oxygen permeable membrane and oxygen/carbon monoxide mixed gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5478444A (en) * | 1992-05-11 | 1995-12-26 | Gas Research Institute | Composite mixed ionic-electronic conductors for oxygen separation and electrocatalysis |
| CN1121257C (en) * | 1999-11-08 | 2003-09-17 | 中国科学技术大学 | Ceramic material for making compact oxygen-permeable separation membrane and and its oxygen permeable membrane separator |
| CN1180879C (en) * | 2002-06-27 | 2004-12-22 | 中国科学院大连化学物理研究所 | Two-phase mixed conductor oxygen-breathable film |
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