CN116425524A - Multi-halogen doped high-oxygen flux perovskite membrane and preparation method and application thereof - Google Patents
Multi-halogen doped high-oxygen flux perovskite membrane and preparation method and application thereof Download PDFInfo
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- 239000001301 oxygen Substances 0.000 title claims abstract description 114
- 239000012528 membrane Substances 0.000 title claims abstract description 85
- 230000004907 flux Effects 0.000 title claims abstract description 49
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 90
- 238000000034 method Methods 0.000 claims abstract description 59
- 239000000463 material Substances 0.000 claims abstract description 49
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 14
- 238000000462 isostatic pressing Methods 0.000 claims abstract description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 7
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 7
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 7
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000005245 sintering Methods 0.000 claims description 17
- 238000003746 solid phase reaction Methods 0.000 claims description 13
- 238000000498 ball milling Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
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- 238000005049 combustion synthesis Methods 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
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- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 2
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- 239000000843 powder Substances 0.000 abstract description 25
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- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000007790 solid phase Substances 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 description 27
- 150000002367 halogens Chemical class 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- -1 oxygen ion Chemical class 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 229910052794 bromium Inorganic materials 0.000 description 5
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- 239000012071 phase Substances 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
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- 150000005309 metal halides Chemical class 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
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- 229910016036 BaF 2 Inorganic materials 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 description 2
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- 150000001450 anions Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
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- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 229910017768 LaF 3 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
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Abstract
The invention provides a multi-halogen doped high-oxygen flux perovskite membrane and a preparation method and application thereof, and belongs to the technical field of mixed conductor oxygen permeable membranes. The general formula of the material is A x A’ 1‑ x B y B’ 1‑y O 2.9‑δ X 0.1 Wherein A, A 'is independently a rare earth metal element or an alkaline earth metal element, B, B' is independently a transition metal element, X is two or more than two of F, cl, br, I, delta is the oxygen non-stoichiometric coefficient of the material, X is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1. By solid phase inversionThe material powder is synthesized by methods such as a reaction method, and the like, and the oxygen permeable membrane material is prepared by using a membrane preparation technology including but not limited to an isostatic pressing method and is obtained by secondary roasting. The oxygen permeable membrane prepared by the method has higher oxygen permeation flux than undoped membrane materials, and the halide of metal ions is cheap and easy to obtain, so that the method can be widely applied to the preparation process of the oxygen permeable membrane materials.
Description
Technical Field
The invention relates to the technical field of mixed conductor oxygen permeable membranes, in particular to a multi-halogen doped high-oxygen flux perovskite membrane, and a preparation method and application thereof.
Background
In recent years, research in the field of material science has achieved a leap development, in which mixed conductor materials have been receiving attention in the fields of solid oxygen fuel cells, electrocatalytic oxidation, and high purity oxygen production, with excellent ion and electron transport properties. In the preparation process of high-purity oxygen, the perovskite type mixed conductor oxygen permeation membrane material is expected to become one of the most economical and development potential technologies due to the advantages of low energy consumption and cost, high oxygen production purity (more than 99 percent) and the like. At present, one of the challenges in realizing the industrialization of perovskite type oxygen permeable membrane technology is to find a membrane material with more excellent oxygen permeable performance, and solve the problem of low oxygen permeation flux at medium and low temperatures.
In the past three decades, mixed conductor oxygen permeable membranes have been under intensive research in the academia, and perovskite mixed conductor oxygen permeable membrane materials have made certain progress in oxygen permeation and stability. However, the mixed conductor oxygen permeable membranes still face a number of challenges, such as low oxygen permeation flux of perovskite materials at medium and low temperatures during the production of high purity oxygen. There is therefore a need to further explore more superior material design strategies to develop perovskite mixed conductor oxygen permeable membrane materials with superior properties.
Disclosure of Invention
The invention aims to provide a multi-halogen doped high-oxygen flux perovskite membrane, and a preparation method and application thereof, so as to solve the technical problem of low oxygen permeation flux of a mixed conductor oxygen permeation membrane at low temperature in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a multi-halogen doped high oxygen flux perovskite membrane, the general formula of which is A x A’ 1-x B y B’ 1-y O 2.9-δ X 0.1 Wherein A, A 'is independently a rare earth metal element or an alkaline earth metal element, B, B' is independently a transition metal element, X is two or more than two of F, cl, br, I, delta is the oxygen non-stoichiometric coefficient of the material, X is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1.
Further, the rare earth metal element comprises one or more of La, pr, nd and Sm; the alkaline earth metal element comprises one or more of Gd, ba and Sr; the transition metal element contains one or more of Ni, cu, zn, co, fe, ce, cr, al and Ga.
The invention provides a preparation method of a multi-halogen doped high-oxygen flux perovskite membrane, which comprises the following steps:
1) Weighing the raw materials according to the stoichiometric ratio, carrying out a mixing reaction, and presintering the mixed materials to obtain a film material;
2) And (3) forming the membrane material to obtain an oxygen permeable membrane precursor, and roasting the oxygen permeable membrane precursor to obtain the multi-halogen doped high-oxygen flux perovskite membrane.
Further, in the step 1), the mixing reaction includes one of a solid phase reaction method, a solution gel method, a hydrothermal synthesis method, a wet chemical method, a combustion synthesis method, and a supercritical drying method.
Further, in the solid phase reaction method, the rotation speed of ball milling is 300-500 rpm, the time of ball milling is 12-48 hours, and the dispersion medium in the ball milling is absolute ethyl alcohol.
Further, in the step 1), the pre-sintering temperature is 800-1100 ℃, the pre-sintering time is 5-10 h, and the temperature rising rate from the room temperature to the pre-sintering temperature is 2-5 ℃/min; the temperature reduction rate of the presintering temperature to the room temperature is 2-5 ℃/min.
Further, the shaping includes one of an isostatic pressing method, a plastic extrusion method, and a phase inversion method.
Further, the molding pressure is 10-30 MPa, and the pressure maintaining time is 2-10 min.
Further, the temperature of the roasting treatment is 1100-1300 ℃, the time of the roasting treatment is 8-10 h, and the temperature rising rate is 2-5 ℃/min.
The invention also provides an application of the meta-halogen doped high-oxygen flux perovskite membrane in oxygen separation.
The invention has the beneficial effects that:
optimization of oxygen permeation performance and stability of membrane materials is typically achieved by manipulating the crystal structure properties of the membrane material (e.g., oxygen vacancy concentration, gate size, unit cell free volume, and metal-oxygen average bond energy). For example, for perovskite oxygen permeable membranes, the bond energy size of A-O/B-O directly affects the ease of oxygen defect formation and its migration performance. In other words, when the binding energy of the metal ion to the oxygen ion is weaker, the oxygen ion is more likely to break loose the binding of the metal ion to form oxygen vacancies. Thus, the lower the average binding energy (ABE, average metal-oxygenbond energy) of the metal-oxygen bond (M-O bond), the more advantageous the formation of oxygen vacancies and the migration of oxygen ions. Research shows that anion doping is an effective strategy based on the traditional perovskite oxide doping strategy, and different anions are introduced to have influence on the aspects of crystal structure, bulk diffusion property, surface exchange property, ion binding energy and the like of the perovskite material.
The invention selects two or more than two of halogen elements of fluorine, chlorine, bromine and iodine for doping, wherein fluorine ions have stronger electron-withdrawing cloud effect as ions with highest electronegativity in the periodic table of elements, and the ion radius is close to the oxygen ion radius, so that the position of oxygen ions in a unit cell can be partially replaced, and electron cloud near the oxygen ions can be reduced after doping, thereby reducing metal-oxygen bond energy and enabling the oxygen ions to be easier to desorb. And secondly, chlorine, bromine and iodine elements have larger atomic radius than oxygen elements, and doping can expand cells to cause the increase of cell parameters, and for materials with grain boundaries blocking oxygen ion transmission, the increase of cell parameters can effectively reduce the resistance of oxygen ion transmission at the boundaries of the cells, so that the oxygen transmission rate of the materials is further improved. The multi-halogen doped oxygen permeation membrane prepared by the method has higher oxygen permeation flux than the membrane without halogen doping, and the corresponding halide of metal ions is cheap and easy to obtain, so that the multi-halogen doped oxygen permeation membrane can be widely applied to the preparation process of oxygen permeation membrane materials.
Drawings
FIG. 1 shows the Ba prepared in example 1 and comparative example 1 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 2.9-δ Cl 0.06 F 0.04 、Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 2.9-δ Cl 0.10 Oxygen permeation flux contrast diagram of the sheet membrane at 650-900 ℃;
FIG. 2 shows the Ba prepared in example 1 and comparative example 2 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 2.9-δ Cl 0.06 F 0.04 、Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 2.9-δ F 0.10 Oxygen permeation flux contrast diagram of the sheet membrane at 650-900 ℃;
FIG. 3 shows the Ba prepared in example 1 and example 2 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 2.9-δ Cl 0.06 F 0.04 、Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 2.9-δ Cl 0.04 F 0.06 X-ray diffraction pattern of the sheet film after sintering at 950 ℃ for 5 hours;
FIG. 4 is a graph of the microtopography of the sheet membranes prepared in example 1 and example 2 sintered at 1100℃for 10 hours;
FIG. 5 is a graph showing the oxygen permeation flux of the sheet type membranes prepared in example 1 and example 2 according to the temperature;
FIG. 6 is SrCo prepared in example 3 0.8 Fe 0.2 O 2.9-δ Cl 0.05 F 0.05 Sintering the sheet membrane at 1080 ℃ for 5 hours;
FIG. 7 shows La prepared in example 4 0.5 Pr 0.5 Fe 0.8 Mn 0.2 O 2.9-δ F 0.04 Cl 0.04 Br 0.02 FIG. of the overflow of F, cl and Br species with temperature in hollow fiber membranes.
Detailed Description
The invention provides a multi-halogen doped high oxygen flux perovskite membrane, the general formula of which is A x A’ 1-x B y B’ 1-y O 2.9-δ X 0.1 Wherein A, A 'is independently a rare earth metal element or an alkaline earth metal element, B, B' is independently a transition metal element, X is two or more than two of F, cl, br, I, delta is the oxygen non-stoichiometric coefficient of the material, X is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1.
In the present invention, X is preferably two or more of F, cl and Br, and more preferably F and Cl.
In the present invention, x is preferably 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9; y is preferably 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9.
In the present invention, the rare earth metal element contains one or more of La, pr, nd and Sm, preferably one or more of La, pr and Nd, and more preferably La and/or Pr.
In the present invention, the alkaline earth metal element contains one or more of Gd, ba and Sr, preferably Gd and/or Ba, further preferably Gd.
In the present invention, the transition metal element contains one or more of Ni, cu, zn, co, fe, ce, cr, al and Ga, preferably one or more of Ni, cu, zn, co, fe and Ce, and more preferably one or more of Ni, cu and Zn.
The invention provides a preparation method of a multi-halogen doped high-oxygen flux perovskite membrane, which comprises the following steps:
1) Weighing the raw materials according to the stoichiometric ratio, carrying out a mixing reaction, and presintering the mixed materials to obtain a film material;
2) And (3) forming the membrane material to obtain an oxygen permeable membrane precursor, and roasting the oxygen permeable membrane precursor to obtain the multi-halogen doped high-oxygen flux perovskite membrane.
In the invention, the introduction modes of the X element are respectively as follows: the halide corresponding to the introduction of Cl element is ACl n 、A’Cl n 、BCl n 、B’Cl n The method comprises the steps of carrying out a first treatment on the surface of the The introduction of Br element corresponds to a halide of ABr n 、A’Br n 、BBr n 、B’Br n The method comprises the steps of carrying out a first treatment on the surface of the The introduction of element I corresponds to the halide being AI n 、A’I n 、BI n 、B’I n Wherein n is the valence of the corresponding stable compound of the metal cation.
In the present invention, in the step 1), the mixing reaction includes one of a solid phase reaction method, a solution gel method, a hydrothermal synthesis method, a wet chemical method, a combustion synthesis method, and a supercritical drying method, and is preferably a solid phase reaction method.
In the solid phase reaction method, the rotation speed of the ball milling is 300-500 rpm, preferably 400rpm; the ball milling time is 12-48 h, preferably 24h; the dispersion medium in ball milling is absolute ethyl alcohol.
In the present invention, in the step 1), the pre-sintering temperature is 800 to 1100 ℃, preferably 900 to 1000 ℃, and more preferably 950 ℃; the pre-sintering time is 5-10 hours, preferably 6-8 hours, and more preferably 7 hours; the temperature rising rate from room temperature to the pre-sintering temperature is 2-5 ℃/min, preferably 3-4 ℃/min; the cooling rate of the presintering temperature to room temperature is 2-5 ℃/min, preferably 3-4 ℃/min.
In the present invention, the molding includes one of an isostatic pressing method, a plastic extrusion method, and a phase inversion method, and preferably an isostatic pressing method.
In the present invention, the molding pressure is 10 to 30MPa, preferably 15 to 25MPa, and more preferably 20MPa; the dwell time is 2 to 10min, preferably 5min.
In the present invention, the temperature of the calcination treatment is 1100 to 1300 ℃, preferably 1150 to 1250 ℃, and more preferably 1200 ℃; the roasting treatment time is 8-10 h, preferably 9h; the heating rate is 2-5 ℃/min, preferably 3-4 ℃/min.
In the invention, the prepared meta-halogen doped high oxygen flux perovskite film needs to have the density of more than 95% to perform an oxygen permeation experiment.
The invention also provides an application of the meta-halogen doped high-oxygen flux perovskite membrane in oxygen separation.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Preparation of the high oxygen flux perovskite film Ba of the invention Using solid phase reaction method 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 2.9-δ Cl z F 0.1-z Wherein z is 0.06. Weighing a metal salt BaCO of a target mass using an analytical balance 3 、SrCO 3 、Co 2 O 3 And Fe (Fe) 2 O 3 Halogen is passed through the corresponding metal halide SrCl 2 、SrF 2 Absolute ethanol is added as a dispersion medium, and ball milling is carried out for 24 hours at a rotating speed of 300r/min by using a planetary ball mill. Transferring the blended powder into a culture dish, placing the culture dish in an oven, drying at 70 ℃ for 24 hours, and sieving the powder by a 100-mesh sample sieve to avoid powder agglomeration. And heating the raw material powder to 950 ℃ in a muffle furnace, preserving heat for 5 hours, and cooling to room temperature to obtain the corresponding perovskite powder, wherein the heating rate and the cooling rate are 2 ℃/min.
The sheet membrane is prepared by an isostatic pressing method. The powder prepared above is transferred to an agate mortar after being sieved by a 300-mesh sieve, and PVA is added as a binder for uniform grinding. The powder was compressed by applying a radial pressure of 15Mpa using a die with a diameter of 16 mm. Placing the membrane in a high-temperature muffle furnace, heating to 1100 ℃ and sintering for 8 hours to obtain a compact sheet membrane, wherein the heating rate and the cooling rate are both 2 ℃/min, and sintering to prepare the compact sheet membrane.
Comparative example 1
Preparation of single halogen doped perovskite film Ba using solid phase reaction method 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 2.9-δ Cl 0.1 The preparation method is the same as in example 1.
The prepared membrane exhibits a typical perovskite crystal form, and the membrane is polished to 1mm for oxygen permeability performance testing, as shown in fig. 1. Sheet type membrane oxygen flux at 650 ℃ is 0.31ml/min/cm 2 Oxygen permeation flux at 900℃was 1.36ml/min/cm 2 . Compared to the oxygen permeation flux of the binary halogen doped sheet membrane (example 1), the oxygen flux of the mono-halogen Cl doping is lower in the test temperature range than the binary halogen co-doped sheet membrane。
Comparative example 2
Preparation of single halogen doped perovskite film Ba using solid phase reaction method 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 2.9-δ F 0.1 The preparation method is the same as in example 1. XRD testing was performed on the sheet membrane, exhibiting a typical perovskite phase structure, and oxygen permeation performance was tested by polishing to 1mm, the test results being shown in fig. 2. Sheet type membrane oxygen flux at 650 ℃ is 0.57ml/min/cm 2 Oxygen permeation flux at 900℃was 2.34ml/min/cm 2 . In contrast to the oxygen permeation flux of the binary halogen doped monolithic membranes (example 1), the oxygen flux of the monohalogen F doped monolithic membranes was lower than the binary halogen co-doped monolithic membranes over the test temperature range.
Example 2
Preparation of high oxygen flux perovskite film Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 2.9-δ Cl z F 0.1-z Wherein z is 0.04, the preparation is the same as in example 1.
The X-ray diffraction test results of the dense films of example 1 and example 2 are shown in fig. 3, and the materials each formed a typical perovskite crystal structure with only slight differences in the characteristic peak positions. The scanning electron microscope image of the film surface is shown in fig. 4, the boundary of the grain boundary is clear, no second phase is generated, and the surface presents a compact structure.
The sheet membrane was polished to 1mm with 800 mesh metallographic sandpaper for oxygen permeation experiments. FIG. 5 shows the oxygen permeation flux of the material at different temperatures, compared with Ba without binary halogen doping 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ Compared with the material, the oxygen permeation flux of the doped material reaches 2.9ml/min/cm at most 2 The oxygen flux is improved by 60 percent.
Example 3
Preparation of the high oxygen flux perovskite film SrCo of the present invention Using solid phase reaction method 0.8 Fe 0.2 O 2.9-δ Cl 0.05 F 0.05 Weighing a metal salt SrCO of a target mass using an analytical balance 3 、Co 2 O 3 And Fe (Fe) 2 O 3 Halogen is passed through the corresponding metal halide SrCl 2 、SrF 2 Absolute ethanol is added as a dispersion medium, and a planetary ball mill is used for ball milling for 24 hours at a rotating speed of 400 r/min. Transferring the blended powder into a culture dish, placing the culture dish in an oven, drying at 70 ℃ for 24 hours, and sieving the powder by a 100-mesh sample sieve to avoid powder agglomeration. And heating the raw material powder to 850 ℃ in a muffle furnace, preserving heat for 10 hours, and cooling to room temperature to obtain the corresponding perovskite powder, wherein the heating rate and the cooling rate are 2 ℃/min.
The sheet membrane is prepared by adopting a cold sintering method. SrCo 0.8 Fe 0.2 O 2.9-δ Cl 0.05 F 0.05 The powder is transferred to an agate mortar after passing through a 300-mesh sieve, and deionized water is added for uniform grinding. And (3) applying radial pressure of 20Mpa to a die with the diameter of 16mm, preserving heat for 2 hours at 200 ℃, tabletting the powder, and placing the film in a high-temperature muffle furnace, heating to 1080 ℃ and sintering for 5 hours to obtain the compact sheet type film, wherein the heating rate and the cooling rate are both 2 ℃/min.
Dense SrCo 0.8 Fe 0.2 O 2.9-δ Cl 0.05 F 0.05 The crystal structure of the sheet membrane exhibits a good perovskite phase structure. The scanning electron microscope image of the surface and the section of the diaphragm is shown in figure 6, the section has no through holes, and the surface presents a compact structure.
SrCo 0.8 Fe 0.2 O 2.9-δ Cl 0.05 F 0.05 The sheet membrane was polished to 1mm with 800 mesh metallographic sandpaper for oxygen permeation experiments. From the results, it can be seen that SrCo is co-doped with fluorine and chlorine 0.8 Fe 0.2 O 3-δ Compared with the material, the oxygen permeation flux of the doped material is improved by 40 percent.
Example 4
Preparation of the high oxygen flux perovskite film La of the present invention Using solid phase reaction 0.5 Pr 0.5 Fe 0.8 M 0.2 O 2.9-δ F 0.04 Cl 0.04 Br 0.02 Weighing a metal salt La of a target mass using an analytical balance 2 O 3 、Pr 2 O 3 And Fe (Fe) 2 O 3 MnO, halogen through corresponding metal halide LaCl 3 、LaF 3 、LaBr 3 Absolute ethanol is added as a dispersion medium, and a planetary ball mill is used for ball milling for 24 hours at the rotating speed of 350 r/min. Transferring the blended powder into a culture dish, placing the culture dish in an oven, drying at 70 ℃ for 24 hours, and sieving the powder by a 100-mesh sample sieve to avoid powder agglomeration. And heating the raw material powder to 900 ℃ in a muffle furnace, preserving heat for 10 hours, and cooling to room temperature to obtain the corresponding perovskite powder, wherein the heating rate and the cooling rate are 5 ℃/min.
Hollow fiber membranes were prepared using a phase inversion method. La (La) 0.5 Pr 0.5 Fe 0.8 Mn 0.2 O 2.9-δ F 0.04 Cl 0.04 Br 0.02 And (3) placing the hollow fiber membrane in a high-temperature muffle furnace, heating to 1230 ℃ and sintering to obtain the hollow fiber membrane, wherein the heating rate and the cooling rate are 5 ℃/min.
La 0.5 Pr 0.5 Fe 0.8 Mn 0.2 O 2.9-δ F 0.04 Cl 0.04 Br 0.02 The crystal structure exhibits a good perovskite phase structure. La is subjected to 0.5 Pr 0.5 Fe 0.8 Mn 0.2 O 2.9-δ F 0.04 Cl 0.04 Br 0.02 Is used for oxygen permeation experiments. Co-doping La with fluorine, chlorine and bromine 0.5 Pr 0.5 Fe 0.8 Mn 0.2 O 3-δ Compared with the material, the oxygen permeation flux of the doped material is greatly improved, and the overflow condition of F, cl element is detected by adopting an online mass spectrum, as shown in fig. 5, F, cl species are not detected in the signal, which indicates that F, cl element can stably exist in perovskite oxide.
Example 5
Preparation of high oxygen flux perovskite Ba of the invention Using solution gel method 0.5 Zr 0.5 Ce 0.8 Ti 0.2 O 2.9-δ F 0.08 I 0.02 Sheet membrane, nitrate Ba (NO) of target mass was weighed using analytical balance 3 ) 2 、Zr(NO 3 ) 4 And Fe (NO) 3 ) 3 ·9H 2 O and tetrabutyl titanate (C) 16 H 36 O 4 Ti), halogen through the corresponding metal halide BaCl 2 、BaF 2 Introduction of tetrabutyl titanate (C 16 H 36 O 4 Ti) and citric acid CA in a molar ratio of 1:5 in deionized water at 80 ℃ until the solution is clear, and then adding a stoichiometric amount of Ba (NO) to the solution 3 ) 2 、Zr(NO 3 ) 4 、Fe(NO 3 ) 3 ·9H 2 O、BaI 2 、BaF 2 . EDTA and citric acid CA are taken as complexing agents, total metal ions/EDTA/CA are added according to the mol ratio of 1:1:2, and then NH is added 3 ·H 2 O was added to the solution and the pH was adjusted to 6.5. The transparent gel was prepared by stirring at 90 ℃. Then, the mixture was heated in an oven at 300℃for 5 hours. And finally, heating the raw material powder to 1000 ℃ in a muffle furnace, preserving heat for 10 hours, and cooling to room temperature to obtain the corresponding perovskite powder, wherein the heating rate and the cooling rate are 5 ℃/min.
The sheet membrane is prepared by an isostatic pressing method. Ba (Ba) 0.5 Zr 0.5 Ce 0.8 Ti 0.2 O 2.9-δ F 0.08 I 0.02 The powder is transferred to an agate mortar after passing through a 300-mesh sieve, and PVA is added for uniform grinding. And (3) applying radial pressure of 20Mpa to the powder by using a die with the diameter of 16mm, tabletting, and placing the film in a high-temperature muffle furnace, heating to 1150 ℃ and sintering to obtain the compact sheet type film, wherein the heating rate and the cooling rate are 2 ℃/min.
For Ba 0.5 Zr 0.5 Ce 0.8 Ti 0.2 O 2.9-δ F 0.08 I 0.02 The sheet membrane is subjected to X-ray diffraction test, and the perovskite structure is complete, and the phase structure is not obviously changed before and after doping. The oxygen permeation flux of the material at different temperatures is tested, and the test result shows that the fluorine-iodine co-doped sheet membrane prepared by the solution gel method has higher oxygen permeation flux than the undoped material and still has 0.6ml/min/cm at 650 DEG C 2 Is not doped with the parent material Ba 0.5 Zr 0.5 Ce 0.8 Ti 0.2 O 3-δ Is only 0.34ml/min/cm 2 The oxygen permeability of the fluorine-iodine co-doped material is improved by 76.5 percent at low temperature.
From the above examples, the present invention provides a multi-halogen doped high oxygen flux perovskite membrane, a preparation method and applications thereof. The invention synthesizes material powder by adopting methods such as a solid phase reaction method, a solution gel method, a hydrothermal synthesis method, a wet chemical method, a combustion synthesis method, a supercritical drying method and the like, prepares an oxygen permeable membrane material by using membrane preparation technologies including but not limited to an isostatic pressing method, a plastic extrusion method and a phase inversion method, and obtains a multi-element halogen doped perovskite membrane material by secondary roasting. The oxygen permeable membrane prepared by the method has higher oxygen permeation flux than undoped membrane materials, and the halide of metal ions is cheap and easy to obtain, so that the method can be widely applied to the preparation process of the oxygen permeable membrane materials.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A multi-halogen doped high oxygen flux perovskite film is characterized in that the general formula is A x A’ 1-x B y B’ 1-y O 2.9-δ X 0.1 Wherein A, A 'is independently a rare earth metal element or an alkaline earth metal element, B, B' is independently a transition metal element, X is two or more than two of F, cl, br, I, delta is the oxygen non-stoichiometric coefficient of the material, X is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1.
2. The meta-halogen doped high oxygen flux perovskite membrane of claim 1, wherein the rare earth metal element comprises one or more of La, pr, nd and Sm; the alkaline earth metal element comprises one or more of Gd, ba and Sr; the transition metal element contains one or more of Ni, cu, zn, co, fe, ce, cr, al and Ga.
3. A method for preparing the multi-halogen doped high oxygen flux perovskite film according to claim 1 or 2, comprising the following steps:
1) Weighing the raw materials according to the stoichiometric ratio, carrying out a mixing reaction, and presintering the mixed materials to obtain a film material;
2) And (3) forming the membrane material to obtain an oxygen permeable membrane precursor, and roasting the oxygen permeable membrane precursor to obtain the multi-halogen doped high-oxygen flux perovskite membrane.
4. The method according to claim 3, wherein in the step 1), the mixing reaction comprises one of a solid phase reaction method, a solution gel method, a hydrothermal synthesis method, a wet chemical method, a combustion synthesis method and a supercritical drying method.
5. The method according to claim 4, wherein in the solid phase reaction method, the rotation speed of the ball milling is 300-500 rpm, the time of the ball milling is 12-48 hours, and the dispersion medium in the ball milling is absolute ethyl alcohol.
6. The method according to any one of claims 3 to 5, wherein in the step 1), the pre-sintering temperature is 800 to 1100 ℃, the pre-sintering time is 5 to 10 hours, and the heating rate from the room temperature to the pre-sintering temperature is 2 to 5 ℃/min; the temperature reduction rate of the presintering temperature to the room temperature is 2-5 ℃/min.
7. The method of manufacturing according to claim 6, wherein the shaping comprises one of an isostatic pressing method, a plastic extrusion method, and a phase inversion method.
8. The method according to claim 7, wherein the molding pressure is 10 to 30MPa and the holding time is 2 to 10 minutes.
9. The method according to claim 3, 7 or 8, wherein the temperature of the calcination treatment is 1100-1300 ℃, the time of the calcination treatment is 8-10 hours, and the temperature rising rate is 2-5 ℃/min.
10. Use of a multi-halogen doped high oxygen flux perovskite membrane as defined in claim 1 or 2 in oxygen separation.
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