CN1141171C - Prepn of ultrathin self-loaded mixed-conductor oxygen-permeating film - Google Patents
Prepn of ultrathin self-loaded mixed-conductor oxygen-permeating film Download PDFInfo
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Abstract
The present invention relates to a method for manufacturing an ultra-thin self-loading mixed conductor oxygen penetration film. The method comprises the steps that firstly, ultra-fine oxygen penetration film material powder is synthesized by using an EDTA-citric acid combined method; secondarily, on the basis of the ultra-fine oxygen penetration film material powder, a stable collosol suspension containing the material powder, solvents, dispersants, adhesive, plasticizers, organic pore forming agents, etc. is prepared; thirdly, flat plate films which contain different organic pore forming agents with different quantities are made by using a flat plate casting method, and the thickness of the flat plate film is scores of microns; the flat plate films of different kinds are formed and pressed into films; finally, a loading mixed conductor oxygen penetration film composed of an ultra-thin compact layer and a grading porous carrier layer is obtained by strictly controlling sintering temperature processes.
Description
The present invention relates to a kind of method for preparing ultra-thin support type composite conductor oxygen-permeating film, and concrete process conditions have been done to study in great detail.
Composite conductor oxygen-permeating film is causing far-reaching using value is arranged concern widely aspect gas separation and the petrochemical industry.For example, the fuel combustion that is applied to iron and steel and glass industry provides pure oxygen, can reduce energy consumption and atmosphere pollution NO
xDischarge capacity.In addition, in the application of natural gas, oxygen permeation membrane can be used for methane portion oxidation synthesis gas or value-added product such as ethane, ethene.In the pure oxygen preparation field, oxygen permeation membrane is the strong rival of cryogenic separation, pressure swing adsorption method and organic film separation etc.But oxygen permeation membrane can real plant-scale application must possess following characteristics: keep stable chemical constitution under high oxygen permeating amount, high mechanical strength and high chemical stability, the especially reducing atmosphere.After satisfying the first few items characteristics, reduce the operating temperature of stablizing the oxygen flow operation gradually, make the wider of its application.Non-loading type oxygen permeation membrane under the ordinary meaning is difficult to reach above-mentioned these performances, so the two-phase film that constitutes from synthetic support type oxygen permeation membrane (comprising from support type and non-from two kinds of support types), fast oxygen ion conductor and a large amount of noble metal of researcher, adds stability element, exploitation preferably on original perovskite basis and seek new non-perovskite structure new material.Wherein synthetic support type oxygen permeation membrane is the direction that the researcher paid close attention to always, but does not obtain result preferably always.
Yue-Sheng Lin, Deng at document " Oxygen Permeation through Thin MixedConducting Solid Oxide Membranes " AIChE Jouranl, 1994,40 (5), among the 786-798 detailed elaboration the oxygen flow process mechanism of support type oxygen permeation membrane.Chunhua Chen etc. are " Fabrication of La at document
1-xSr
xCoO
3-δThin layers on porous supports by a polymericsol-gel process " J.Mater.Chem.6 (5), 1996, utilize the polymerization sol-gal process at α-Al among the 815-819
2O
3And γ-Al
2O
3Prepare La on the porous carrier
0.3Sr
0.7CoO
3Ultra-thin dense film.United States Patent (USP) 5,683,797 and 5,240,480 grades have also been done research to the support type oxygen permeation membrane, and the result shows the attenuate along with compacted zone, and oxygen permeating amount increases really to some extent, but does not reach the numerical value of theory expectation.Although the researcher utilizes chemical vapour deposition technique, ion sputtering method, brushing method, sol-gel polymerizations method etc. that loaded film has been made extensive work, also can not utilize simply and easily the synthetic various performances of method all preferably from the support type ultrathin membrane.
The object of the present invention is to provide a kind of method that is used for synthetic ultra-thin conceited loaded mixed-conductor oxygen permeation membrane.
To achieve these goals, the method for the ultra-thin support type composite conductor oxygen-permeating film of preparation of the present invention is characterized in that comprising the steps:
A. select the step of suitable oxygen permeable film material,
B. the step for preparing ultra-fine oxygen permeable film material powder,
C. the step for preparing the colloidal sol shape suspension that constitutes by oxygen permeable film material powder, solvent, dispersant, adhesive, plasticizer and organic pore-forming agents etc.,
D. utilize dull and stereotyped casting method to prepare the step that thickness is tens microns ultra-thin flat sheet membrane,
E. prepared flat sheet membrane is carried out dry step,
F. with different types of flat sheet membrane moulding and suppress the step of film forming,
G. control the step that the sintering temperature program obtains ultra-thin support type composite conductor oxygen-permeating film.
In above-mentioned method, it is characterized in that: select suitable oxygen permeation membrane powder for to be: SrCo from molecular formula
0.8Fe
0.2O
3, Ba
xSr
1-xCo
0.8Fe
0.2O
3-δLa
0.6Sr
0.4Co
0.2Fe
0.8O
3, La
0.6Sr
0.4Co
0.2Fe
0.8O
3, La
0.6Sr
0.4Co
0.8Fe
0.2O
3, SrCoFe
0.5O
2-3, Sr
1.7La
0.3Ga
0.6Fe
1.4O
5.15, BaCo
0.4Fe
0.6-xZr
xO
3-δMaterial in one or both, 0＜x in the formula＜0.5,0＜y＜0.5,0＜δ＜0.5.
In above-mentioned steps a, the preparation method of ultra-fine oxygen permeable film material powder adopts solid phase method, citric acid complex method, EDTA acid complexometry or citric acid and EDTA acid to unite a kind of in complexometry or the Cellose macromolecule absorption method method.
In above-mentioned steps c, select organic pore-forming agents in sintering process, can decompose fully and remove, and film remains unchanged when removing organic additive between 300-600 ℃; Common organic pore creating material that decomposes has starch, graphite powder, polyethylene, polypropylene, active carbon or polyethylene glycol.
In above-mentioned steps c, adhesive is among butyryl resin, polyvinyl alcohol, polyvinyl butyral resin, methylcellulose, the epoxy resin etc. and one or more.
In above-mentioned steps c, plasticizer is one or more among the acid of phthalic acid fourth benzyl, repefral, the polyethylene glycol.
In above-mentioned steps c, solvent is one or more the mixture among water, ethanol, isopropyl alcohol, n-butanol, toluene, benzene, acetic acid, heptane and the octane.
In above-mentioned steps c, dispersant is one or more the mixture among Tween 80, glycerine, fish oil, neopelex, polyacrylamide, oleic acid, olein, olein, stearic acid or the tristerin.
In above-mentioned steps c, the preparation process of colloidal sol shape suspension adopts the use of a kind of in mechanical ball milling and the ultrasonic dispersion or the associating of the two.
In above-mentioned steps d, the thickness of casting flat sheet membrane is the 10-100 micron.
In above-mentioned steps e, casting flat sheet membrane drying mode is a kind of in 50 ℃ of dryings or the infrared light radiant drying method in 5 ℃ of dryings in air dry in the air, vacuum drying, the refrigerator, the baking oven.
In above-mentioned steps f, the press temperature of the multi-layer planar mould being made type is between room temperature and 100 ℃, and pressing pressure is between 10-30Mpa.
In above-mentioned method, it is characterized in that: the sintering of moulding back loading film, adopt former powder embedding or not embedding mode, adopt still air or moving air to handle, the combination of one or more modes in the sintering processings such as employing inert gas processing.
In addition, in the preparation method of the invention described above, preferably embodiment is that oxygen permeation membrane powder employing molecular formula is BaCo
0.4Fe
0.6-xZr
xO
3-δMaterial, ultra-fine oxygen permeation membrane powder adopts citric acid and the preparation of EDTA acid associating complexometry, organic pore-forming agents adopts graphite powder, starch and active carbon, adhesive adopts polyvinyl butyral resin, the plasticising type adopts polyethylene glycol, solvent adopts ethanol or isopropyl alcohol, it is Tween 80 that dispersant adopts it, the preparation process of colloidal sol shape suspension adopts the use of uniting of mechanical ball milling and ultrasonic dispersion, casting flat sheet membrane drying mode adopts air dry in the air, the press temperature of the multi-layer planar mould being made type adopts 50 ℃, between the pressing pressure 20-24Mpa, the sintering of moulding back loading film adopts temperature rate lower, different temperature retention times, former powder embedding mode, still air is handled the combination of several middle modes.
The selection of oxygen permeation membrane powder of the present invention is by carrying out material oxygen permeability and Stability Analysis of Structures investigation result.The BaCo of our choosing
0.4Fe
0.4Zr
0.2O
3Oxygen permeating amount be by body phase DIFFUSION CONTROLLED, no matter be at oxidizing atmosphere, reducing atmosphere still all has stability preferably under synthesis gas atmosphere.
The synthetic method of oxygen permeable film material powder has adopted the associating complexometry among the present invention, with EDTA and the common complexing agent of citric acid conduct, comprise nitrate with soluble metallic salt, chloride, acetates etc. are initiation material, with polyethylene glycol, glycerine, lactic acid etc. suppress interionic reunion for dispersant, pH value with nitric acid and ammoniacal liquor regulator solution, system is stirred the thickness colloid that dewaters of evaporation under 80 ℃ of constant temperatures, 150 ℃ solidify the gel powder, under suitable temperature and atmosphere, obtained powder at last in roasting 1-10 hour.
The present invention is that the processes such as sintering that flat sheet membrane that preparation, the casting of flat sheet membranes, the drying of flat sheet membranes, the moulding of flat sheet membranes, the multilayer by superfine powder preparation, the gluey suspension of solubilized stable contains variety classes and varying number organic pore-forming agents is pressed into loaded film presoma and loaded film presoma constitute.Consisting of of the gluey suspension of solubilized stable: isopropyl alcohol, ethanol or the certain proportion mixture of the two are solvent; Tween 80 is a dispersant, and polyvinyl butyral resin is an adhesive, and polyethylene glycol is a plasticizer; Starch or graphite powder are that high temperature can decompose organic pore-forming agents; The flat sheet membrane drying mode is in the still air air dry 30-100 minute; The forming temperature of multi-layer planar film is 50 ℃, between the pressing pressure 20-24Mpa; Loaded film presoma sintering temperature program is that temperature rate is lower, different temperature retention times, and former powder embedding, still air is handled the combination of several modes.
The ultra-thin support type composite conductor oxygen-permeating film of the present invention's preparation adopts ESEM (SEM) to characterize, and the result shows: use the method can synthesize the fine and close load layer of 10-100 micron fast, the carrier layer percent opening is higher, and intensity is better.Use example in detail below.
Below accompanying drawing is carried out simple explanation.
Fig. 1 is BaCo
0.4Fe
0.4Zr
0.2O
3-δXRD spectra.
Fig. 2 is the BaCo of different-thickness
0.4Fe
0.4Zr
0.2O
3-δThe oxygen permeation membrane oxygen permeating amount is with the variation of temperature curve map.
Fig. 3 is that various atmosphere are handled back BaCo
0.4Fe
0.4Zr
0.2O
3-δXRD spectra.A wherein: pure oxygen atmosphere 100 hours, b: straight argon atmosphere 100 hours, c:5.05vol% hydrogen and 94.95vol% argon atmospher 100 hours, 1vol% oxygen is 5 hours then.
The exterior view of fine and close load layer Electronic Speculum when Fig. 4 is pore creating material for starch.
The sectional drawing of porous carrier layer Electronic Speculum when Fig. 5 is pore creating material for starch.
The exterior view of fine and close load layer Electronic Speculum when Fig. 6 is pore creating material for graphite powder.
The sectional drawing of porous carrier layer Electronic Speculum when Fig. 7 is pore creating material for graphite powder.
Give further detailed explanation below by embodiment and accompanying drawing to technology of the present invention.
Adopt citric acid and EDTA acid associating complexometry to synthesize BaCo
0.4Fe
0.4Zr
0.2O
3-δThe composite conductor oxygen-permeating film material.Take by weighing EDTA acid 80 grams, citric acid 100 grams are dissolved under the heating condition in the 300ml concentrated ammonia liquor; Add 0.2mol Ba (NO
3)
2, 0.08mol Co (NO
3)
2, 0.08mol Fe (NO
3)
3With 0.04mol Zr (NO
3)
4Solution; Be heated to 80 ℃, constant temperature stirs then, gets a transparent hot melt colloid along with the evaporation of moisture is last, and colloid is handled some hrs under 200 ℃, gets powder in 5 hours 950 ℃ of roastings at last.The XRD powder diffraction method is measured and is shown the cubic perovskite structure composite oxides that formed pure phase, as shown in Figure 1.
The BaCo of different-thickness
0.4Fe
0.4Zr
0.2O
3-δThe mensuration of composite conductor oxygen-permeating film oxygen permeating amount is polished diaphragm with SiC sand paper both sides, final diaphragm thickness is that 1.0-1.5mm adopts inorganic ceramic glue to seal.The osmotic cell outer tube leads to synthesis of air, and flow velocity is 150ml/min, and the logical high-purity helium (99.995%) of interior pipe purges, and flow velocity is 30ml/min.Fig. 2 expresses the BaCo of different-thickness
0.4Fe
0.4Zr
0.2O
3-δThe oxygen permeation membrane oxygen permeating amount is with the variation of temperature curve.Can find out obviously that by Fig. 2 oxygen permeating amount increases with the rising of temperature, and the 1.00ml/cm that has proposed with professor Steele
2Min is close.
Embodiment 3
BaCo
0.4Fe
0.4Zr
0.2O
3-δThe structural stability of oxygen permeable film material is measured.Utilize the stability of oxidizing atmosphere, inert atmosphere and reducing atmosphere experimental material.Material is used high-purity O down at 800 ℃
2Purge and drop to room temperature in same atmosphere after 100 hours and carry out the structural analysis material; Material drops to room temperature in same atmosphere and carries out structural analysis after purging 100 hours with high-purity Ar under 800 ℃; Material is used 5%volH earlier at 800 ℃
2Purged 100 hours with the 95%volAr gaseous mixture, use 1%O then
2Carry out oxidation with the 99%Ar gaseous mixture and recover, drop to room temperature at this mixed atmosphere afterwards and carry out structure determination, as shown in Figure 3.The result shows BaCo
0.4Fe
0.4Zr
0.2O
3-δThe pure phase cubic perovskite structure that oxygen permeable film material still is kept perfectly is all to show the reversible stability of splendid structure in oxidizing atmosphere or in reaching reducing atmosphere.
Embodiment 4
The preparation process of the gluey suspension of solubilized stable.
The choice of Solvent choice of Solvent by other of colloidal sol shape suspension form, flat sheet membrane rate of drying and thickness determined.Experimental result shows that water is not a kind of good solvent for preparing ultra-thin flat sheet membrane, and this is because water is a kind of solvent of difficult volatilization, and the dry temperature that need be long-time and higher of flat sheet membrane makes that synthetic flat sheet membrane is thicker.Have more high-volatile organic solvent, be selected as solvent and made The effect as ethanol, isopropyl alcohol, n-butanol and toluene or certain two kinds the mixture in them.The result shows that isopropyl alcohol or isopropyl alcohol and a certain amount of alcohol mixture obtained effect preferably.
Although the consumption of dispersant is very little during the selection of dispersant preparation colloidal sol shape suspension, it plays crucial effects to the stability of suspension.We have selected a large amount of dispersants to do trial in preparation colloidal sol shape suspension process.The result shows, Tween 80 is a dispersant preferably, and its optimum amount is 0.7～2.5% of a solid matter quality, and in addition, the kind of organic pore-forming agents and addition have very big influence to the consumption of dispersant.
The selection experimental result of adhesive and plasticizer shows that polyvinyl butyral resin and polyethylene glycol are a pair of adhesive preferably and plasticizer.The total consumption of the two is about 10% to 40% of solid oxidation powder and organic additive gross mass.Generally binder dosage is that plasticizer consumption twice left and right sides Shi Hui obtains flat sheet membrane preferably.The kind of organic pore-forming agents and consumption having a significant impact in addition to adhesive and plasticizer with consumption.
Can decompose the selection of organic pore-forming agents and select conducts such as graphite powder, starch, polyethylene and polypropylene can decompose organic pore-forming agents, improve the percent opening of carrier layer.Experimental result shows that these several organic matters can be used as pore creating material.But their character has a significant impact the formation of colloidal sol shape suspension, when pore creating material is graphite powder, along with the increase of pore creating material addition, needs the amount of organic bond and organic plasticizer also to increase gradually; When starch is organic pore-forming agents,, need the amount of organic bond and organic plasticizer but to reduce gradually along with the increase of pore creating material addition.In a word, always add after certain kind and a certain amount of organic pore-forming agents can be by regulating organic bond and organic plasticizer ratio and the consumption of consumption and dispersant etc. make the flat sheet membrane of final preparation have good performance.
According to the above, utilize the BaCo of citric acid and EDTA acid associating complexometry preparation
0.4Fe
0.4Zr
0.2O
3-δPowder is ball milling 10 hours at first, adds organic pore-forming agents graphite powder or starch and solvent isopropyl alcohol then, with Tween 80 as dispersant.At room temperature stirred 5 hours with magnetic stirring apparatus, add the adhesive polyethylene butyral afterwards and become to mould the agent polyethylene glycol and stir the 10 hours final stable sols shape suspension that forms again.
Embodiment 5
The casting of flat sheet membrane.Stable sols shape suspension synthetic among the embodiment 4 is cast on the plate carrier uniformly, utilize methods such as air at room temperature atmosphere, 50 ℃ of baking ovens, 5 ℃ of refrigerators and infra-red radiation to carry out drying respectively.The result shows that the effect of drying means is better in the room temperature still air.
Embodiment 6
The flat sheet membrane that obtains among the embodiment 5 is processed into the disk shape, then different types of dull and stereotyped diaphragm is placed on compression moulding in the stainless steel mould.Press temperature is 40-90 ℃, and pressing pressure is 20-25Mpa, and the press time is 10-40 minute.
Embodiment 7
The sintering temperature program of loaded film presoma.The sintering temperature program of loaded film presoma is the committed step of the ultra-thin support type composite conductor oxygen-permeating film of preparation.Through experimental selection repeatedly the program of sintering preferably as shown in table 1.
The sintering temperature program of table 1 support type oxygen permeation membrane
The SEM of embodiment 8 ultra-thin support type composite conductor oxygen-permeating films characterizes
| Temperature range (℃) | Heating rate (℃/min) | Rate of temperature fall (℃/min) | Temperature retention time (min) |
| 20-300 | 0.3 | ||
| 300 | 100 | ||
| 300-600 | 0.5 | ||
| 600 | 300 | ||
| 600-800 | 0.5 | ||
| 800 | 120 | ||
| 800-1150 | 1 | ||
| 1150 | 600 | ||
| 1150-800 | 0.5 | ||
| 800 | 60 | ||
| 800-400 | 1 | ||
| 400 | 100 | ||
| 400-20 | Naturally cooling |
The density of the load layer of ultra-thin support type composite conductor oxygen-permeating film and the percent opening of carrier layer have been made The effect with SEM.Starch and graphite powder are as pore creating material; The consumption of organic additive is about 25% of gross weight approximately; The dispersant Tween 80, the weight ratio of plasticizer PEG400 and adhesive polyethylene butyral is 1: 3: 6.The addition of load layer pore creating material is 15%.It is the surperficial SEM picture of the load layer of pore creating material that Fig. 4 and Fig. 6 have provided respectively with starch and graphite powder, and the result shows that complete compact surfaces layer forms.Fig. 5 and Fig. 7 have provided the characterization result of the load layer that two kinds of pore creating materials produce, visible starch during as pore creating material percent opening lower, and with graphite powder during as pore creating material, percent opening is higher.As seen graphite powder is can decompose organic pore-forming agents preferably.
Comparative example 1
United States Patent (USP), U.S.Patent, 3,330697 (1967), and document " Preparation ofperovskite-type oxide with large surface area by citrate process ", Hua-Min ZHANG, Chem.Lett, P665-668,1987. in this patent and document, adopt citric acid complex method low temperature to synthesize serial low alkali content and contain the perovskite composite oxide powder of Pb series, it is complexing agent that its characteristics are to adopt citric acid, is dispersant with ethylene glycol, has the advantage of low temperature synthesizing high specific surface area composite oxide powder.The formation of single colloid is very sensitive to the pH value, and the control of pH value does not become to be easy to produce precipitation in the glue process fortunately.
Comparative example 2
Electrochemical vapour deposition (EVD) is a kind of method of the commonplace ultra-thin dense form loaded film of preparation, Y.S.Lin, Deng utilizing electrochemical vapor deposition (EVD) on porous alumina carrier, to prepare ultra-thin Y at document " A Kinetic Study of the Electrochemical VaporDeposition of Solid Oxide Electrolyte Films on Porous Substrates; J.Electrochem.Soc.; Vol.137; No.12,1990,3960-3966 "
2O
3Stablize ZrO
2(YSZ) fast oxygen ion conductor dense film.Analyzed the kinetic character of the electrochemical vapour deposition (EVD) process that ultra-thin loaded film generates theoretically on porous carrier.The influence of the aperture of partial pressure of oxygen and carrier to the formation speed of film mainly studied in experimental work.The result shows that the diffusion process of steam and oxygen is the rate determining step of electrochemical vapour deposition (EVD).
Also utilize electrochemical vapor deposition on porous carrier, to prepare ultra-thin Y during U.B.Pal etc. are at document " Electrochemical Vapor Deposition of Yttria-Stabilized Zirconia Films; J.Electrochem.Soc., Vol 137, No.9; 1990,2937-2941 "
2O
3Stablize ZrO
2(YSZ) fast oxygen ion conductor dense film, and the mechanism of electrochemical vapour deposition (EVD) process and the factor that influences the ultrathin membrane performance done investigation.
Comparative example 3
Timothy W.Kueper etc. utilizes sol-gel process to prepare fine and close ultrathin membrane at document in " Thin-film ceramic electrolytes depositedon porous and non-porous substrates by sol-gel techniques; Solid State Ionics52; 1992,251-259 ".Studied the influence of thickness integrality of sol-gel process and carrier character to the support type dense film of preparation, the result show colloidal sol-coagulate than method be a simple synthetic loaded film method.But the difficult preparation of this method is thicker complete fine and close loaded film relatively.
Claims (11)
1. a method for preparing ultra-thin support type composite conductor oxygen-permeating film is characterized in that comprising the steps:
A. from molecular formula be: SrCo
0.8Fe
0.2O
3, Ba
xSr
1-xCo
0.8Fe
0.2O
3-δLa
0.6Sr
0.4Co
0.2Fe
0.8O
3, La
0.6Sr
0.4Co
0.2Fe
0.8O
3, La
0.6Sr
0.4Co
0.8Fe
0.2O
3, SrCoFe
0.5O
2.3, Sr
1.7La
0.3Ga
0.6Fe
1.4O
5.15, BaCo
0.4Fe
0.6-xZr
xO
3-δMaterial in, one or both steps of making oxygen permeable film material are selected in 0＜x in the formula＜0.5,0＜y＜0.5,0＜δ＜0.5,
B. the step for preparing ultra-fine oxygen permeable film material powder,
C. the step for preparing the colloidal sol shape suspension that constitutes by oxygen permeable film material powder, solvent, dispersant, adhesive, plasticizer and organic pore-forming agents etc.,
D. utilize dull and stereotyped casting method to prepare the step that thickness is tens microns ultra-thin flat sheet membrane,
E. prepared flat sheet membrane is carried out dry step,
F. with different types of flat sheet membrane moulding and suppress the step of film forming,
G. control the step that the sintering temperature program obtains ultra-thin support type composite conductor oxygen-permeating film.
2. by the described method of claim 1, it is characterized in that: in the preparation process b of ultra-fine oxygen permeable film material powder, adopt solid phase method, citric acid complex method, EDTA acid complexometry or citric acid and EDTA acid to unite a kind of in complexometry or the Cellose macromolecule absorption method method.
3. by the described method of claim 1, it is characterized in that: selecting organic pore-forming agents in step c is starch, graphite powder, polyethylene, polypropylene, active carbon or polyethylene glycol.
4. by the described method of claim 1, it is characterized in that: adhesive is one or more in butyryl resin, polyvinyl alcohol, polyvinyl butyral resin, methylcellulose or the epoxy resin in step c.
5. by the described method of claim 1, it is characterized in that: plasticizer is one or more of the acid of phthalic acid fourth benzyl, repefral or polyethylene glycol in step c.
6. by the described method of claim 1, it is characterized in that: solvent is one or more the mixture in water, ethanol, isopropyl alcohol, n-butanol, toluene, benzene, acetic acid, heptane and the octane in step c.
7. by the described method of claim 1, it is characterized in that: dispersant is one or more the mixture among Tween 80, glycerine, fish oil, neopelex, polyacrylamide, oleic acid, olein, olein, stearic acid or the tristerin in step c.
8. by the described method of claim 1, it is characterized in that: the preparation process of colloidal sol shape suspension adopts the use of a kind of in mechanical ball milling and the ultrasonic dispersion or the associating of the two in step c.
9. by the described method of claim 1, it is characterized in that: in steps d, the thickness of casting flat sheet membrane is the 10-100 micron.
10. by the described method of claim 1, it is characterized in that: in steps d, casting flat sheet membrane drying mode is a kind of in 50 ℃ of dryings or the infrared light radiant drying method in 5 ℃ of dryings in air dry in the air, vacuum drying, the refrigerator, the baking oven.
11. by the described method of claim 1, it is characterized in that: in step f, the press temperature of the multi-layer planar mould being made type is between room temperature and 100 ℃, and pressing pressure is between 10-30Mpa.
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