CN104752664B - Preparation method of composition for fluorine-containing ion membrane material - Google Patents

Preparation method of composition for fluorine-containing ion membrane material Download PDF

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Publication number
CN104752664B
CN104752664B CN201510124244.5A CN201510124244A CN104752664B CN 104752664 B CN104752664 B CN 104752664B CN 201510124244 A CN201510124244 A CN 201510124244A CN 104752664 B CN104752664 B CN 104752664B
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emulsion
fluorine
fluoropolymer
copolymer
tetrafluoroethene
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CN104752664A (en
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付铁柱
周强
汪星平
孙倍佳
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Juhua Group Technology Centre
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention relates to a preparation method of a composition for a fluorine-containing ion membrane material. A fluorine-containing polymer and fluorine-containing ion polymer composition is acquired by virtue of the processes of blending, co-condensation, washing, drying and the like for a fluorine-containing polymer and a fluorine-containing ion polymer emulsion. According to the invention, the process is simple, the industrialization is easy to realize, the composition components are uniformly mixed, the prepared composition is good in mechanical property, the proton conductivity is more than or equal to 10＜-2＞S/cm＜2＞, and a membrane which is made of the composition can be used for the fields such as chlor-alkali, fuel cells, lithium batteries and solid super acidic catalysts.

Description

A kind of preparation method of fluoride ion membrane material composition
Technical field
The present invention relates to field of polymer technology, and in particular to a kind of preparation method of fluoride ion membrane material composition.
Background technology
Fluorine-containing ionic polymer is the polymer containing fluorine element in a kind of main chain or side chain, with excellent thermally-stabilised Property, chemical stability, ionic and highly acid is led, therefore be widely used in chlor-alkali electrolyte membrane, fuel cell ion Exchange membrane, vanadium cell amberplex, lithium battery electrode and barrier film, petrochemical industry solid super acid catalyst etc. are led Domain.At present mainly there are Dupont, Dow chemistry, 3M and Asahi companies of Japan and state in the manufacturer of fluorine-containing ionic polymer Interior Shandong Eastern Mountain, Ju Hua groups etc..
To reduce the cost and price of fluorine-containing ionic polymer, mechanical property is lifted, at present using fluorine-containing ionic polymer Solution impregnation forms enhancement mode fluorine-containing ionic polymer film in microporous support (such as polytetrafluoroethylene (PTFE)), after drying.However, Using the method prepare enhancement mode fluorine-containing ionic polymer film need to prepare the supporter of microcellular structure of uniform pore diameter, perfluor from The multiple tracks technique such as sub- polymer solution, infiltration, drying, preparation process is more complicated, and preparation cost increases；Meanwhile, enhancement mode is fluorine-containing The distribution of fluorine-containing ionic polymer in ionic polymer membranes is affected by the pore-size distribution of micropore supporting layer, and uniformity cannot ensure, And then cause film properties unstable, proton conductivity poor performance.
There is complex process, masking in the enhancement mode exchange membrane containing fluorine prepared to solve above-mentioned current conventional wetting method The problems such as equipment and high technological requirement, a kind of process is simple of urgent need exploration, easy industrialized production, fluorine-containing ionic polymer is in film The preparation method of homodisperse enhancement mode membrane material composition.
The content of the invention
The present invention improves a kind of process is simple, easily low cost, industrialization, product for the deficiencies in the prior art part The preparation method of fluoride ion membrane material composition that can be good.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is：A kind of fluoride ion membrane material combination The preparation method of thing, comprises the following steps：
(a) by weight, by 50～84 parts of fluoropolymer emulsion, fluorine-containing ionic polymer emulsion 16-50 part, Mix under 100～300rpm speeds of agitator, obtain fluoropolymer emulsion compound；
(b) in 25～80 DEG C of temperature, under 100～200rpm speeds of agitator, to the fluoropolymer emulsion that step (a) is obtained Flocculant solution, fluoropolymer emulsion compound breakdown of emulsion is added to form fluoropolymer and fluoride ion polymerization in compound Compositions crude product；
C composition crude product centrifugal dehydration, washing, drying that () obtains step (b), obtain product.
Further：
Described fluoropolymer emulsion be preferably polyvinylidene fluoride homopolymer emulsion, polytetrafluoroethylene (PTFE) homopolymer emulsion, Polychlorotrifluoroehomopolymer homopolymer emulsion, tetrafluoroethene and hexafluoropropylene copolymer emulsion, tetrafluoroethene and ethylene copolymer emulsion, Vinylidene and hexafluoropropylene copolymer emulsion, tetrafluoroethene and perfluoro propyl vinyl ether copolymer emulsion, CTFE With ethylene copolymer emulsion, tetrafluoroethene and perfluoroethylvinyl ether copolymer emulsion, tetrafluoroethene and perfluoromethylvinyl One kind in base ether copolymer emulsion.
The solid content of described fluoropolymer emulsion is preferably 15～30wt.% (wt.% is weight/mass percentage composition).
Described fluorine-containing ionic polymer emulsion is preferably vinylidene and CF2=CF-O-CFCF3CF2-OCF2CF2SO2F Copolymer emulsion, tetrafluoroethene and CF2=CF-O-CFCF3CF2-OCF2CF2SO2F copolymer emulsions, CTFE and CF2= CF-O-CFCF3CF2-OCF2CF2SO2F copolymer emulsions, vinylidene and CF2=CF-O-CF2CF2SO2F copolymer emulsions, four PVF and CF2=CF-O-CF2CF2SO2F copolymer emulsions, CTFE and CF2=CF-O-CF2CF2SO2F copolymers breast Liquid, CTFE and CF2=CF-O-CFCF3CF2-OCF2CF2CF2SO2F copolymer emulsions, tetrafluoroethene and CF2=CF-O- CFCF3CF2-OCF2CF2CF2SO2F copolymer emulsions, vinylidene and CF2=CF-O-CFCF3CF2-OCF2CF2CF2SO2F copolymerization Thing emulsion, vinylidene and CF2=CF-O-CFCF3CF2-OCF2CF2SO2NCH3One kind in copolymer emulsion.
Described fluorine-containing ionic polymer emulsion solid content is preferably 10～30wt.%.
Described flocculant solution is preferably aluminum sulfate aqueous solution, ferric chloride in aqueous solution, ferrous sulfate aqueous solution, calcium chloride One kind in the aqueous solution.
Preferred 2.5.%～the 10wt% of concentration of described flocculant solution.
The addition speed of described flocculant solution is preferably 5g/min～15g/min.
The rotating speed of described centrifugal dehydration is preferably 100～300rpm, and described wash temperature is preferably 25～80 DEG C, institute The drying temperature stated is preferably 80～150 DEG C.
Coacervation process mainly carries out breakdown of emulsion by modes such as high-speed stirred, addition electrolyte flocculant, freezings, by emulsion The process that middle polymer is separated out.Precipitation polymer effect is condensed using high-speed stirred mode poor, and it is big to consume energy；Using freezing side The formula cohesion precipitation polymer time is longer, and it is big to consume energy.Therefore, the present invention uses the mode for adding electrolyte flocculant, by electricity Solution matter is added in emulsion, reduces dissolubility and formation double electrolyte layers of the emulsion ionic emulsifying agent in water, and then makes emulsion Middle polymer is separated out, and the method effect is good, and it is low to consume energy.Described flocculant solution is preferably aluminum sulfate aqueous solution, iron chloride One kind in the aqueous solution, ferrous sulfate aqueous solution, calcium chloride water, the preferred 2.5.% of concentration of described flocculant solution～ 10wt%.
In using addition electrolyte flocculant mode breakdown of emulsion, in addition to the species of flocculant solution, speed, cohesion are added Temperature and stir speed (S.S.) are also to the solidifying of the fluoropolymer in blend composition crude product involved in the present invention and fluorine-containing ionic polymer Poly- speed, yield and fluorine-containing ionic polymer content in the composition and dispersing uniformity have a direct impact.Temperature is too low, wadding Solidifying low yield, flocculation rate is slow；Temperature is too high, and flocculation rate is too fast, fluoropolymer and fluorine-containing ionic polymer skewness, Therefore the temperature of flocculant solution breakdown of emulsion is added to be preferably 25～80 DEG C in the present invention.Add speed and stir speed (S.S.) too fast, wadding Solidifying speed is too fast, there is the fluoropolymer elder generation demulsifying phenomenon that solid content is high, causes fluoropolymer and fluorine-containing ionic polymer point Cloth is uneven, and power consumption is high；Add speed and stir speed (S.S.) too fast, flocculate low yield, flocculation rate is slow, therefore speed is stirred in the present invention Rate is preferably 100～200rpm, and flocculant solution adds speed to be preferably 5g/min～15g/min.
Fluorine-containing ionic polymer has ionic group in the composition crude product obtained due to step (b), easily adsorbs a large amount of Water and a small amount of electrolyte, ionic emulsifying agent, initiator etc., accordingly, it would be desirable to carry out centrifugal dehydration, washing, be dried.Centrifugation Speed is too low, and process efficiency is low；Centrifugation rate is too high, and fluorine-containing ionic polymer is easily migrated in composition so that fluoride ion Polymer dispersion in the composition is uneven, therefore the centrifugation rate in the present invention is preferably 100～300rpm.Due to fluorine-containing Ionomer easily adsorbs substantial amounts of water, and at a certain temperature hygroscopic expansion, has an impact to clean result, therefore the present invention In wash temperature be preferably 25～80 DEG C.Drying temperature is too low, affects drying efficiency；Drying temperature is too high, the group after washing Compound easily forms one layer of compacted zone on surface, equally affect the drying temperature in drying efficiency, therefore the present invention be preferably 80～ 150℃。
The fluoride ion membrane material composition that the present invention is prepared can directly by conventional processing and forming such as extrusion molding Or solution casting method is obtained membrane material, membrane material is after alkali acid conversion (under basic conditions, by sulfuryl fluoride or carboxylate methyl ester base Group is changed into sulfonic acid or carboxylate groups, afterwards under strongly acidic conditions, sulfonic acid or carboxylate groups is converted to into sulfonic acid or carboxylic acid Group), form the fluoropolymer containing acidic-group and fluorine-containing ionic polymer blended membrane material.After the conversion for being obtained Membrane material can be used for the fields such as chlor-alkali, fuel cell, lithium battery, solid super acid catalyst.
Compared with prior art, the present invention has advantages below：
1st, good product performance, the fluoride ion membrane material that the present invention is prepared by parameters such as proportion optimizing, operating conditions Material composition product composition is well mixed, and has both maintained the heat endurance and chemical stability of fluorine-containing ionic polymer, and uses Produce without phenomenon of phase separation in membrane material obtained in the product of the present invention, proton conductivity >=10-2S/cm2, tensile strength exists More than 20.2MPa；
2nd, process is simple, it is easy to operate, easily realize industrialization；
3rd, energy-conserving and environment-protective, three waste discharge is few, meets national environmental protection policy requirements.
Specific embodiment
The present invention is described in further detail with reference to embodiments, but the present invention is not limited solely to following enforcement Example.
Embodiment 1
By polyvinylidene fluoride homopolymer emulsion (solid content 15%) 25kg, vinylidene and CF2=CF-O-CFCF3CF2- OCF2CF2SO2F copolymer emulsions (solid content 10%) 25kg, mixes under 100rpm rotating speeds, obtains fluoropolymer emulsion mixing Material.Then in 25 DEG C of temperature, under 200rpm speeds of agitator, flocculant is added in fluoropolymer emulsion compound with 5g/min Aluminum sulfate solution (2.5wt.%), fluoropolymer emulsion compound breakdown of emulsion forms fluoropolymer and fluorine-containing ionic polymer Composition crude product.By the centrifugal dehydration under 200rpm rotating speeds of above-mentioned composition crude product, then it is washed with deionized water at a temperature of 25 DEG C Wash, then dry at 80 DEG C, obtain composition.
Embodiment 2
By polytetrafluoroethylene (PTFE) homopolymer emulsion (solid content 20%) 30kg, tetrafluoroethene and CF2=CF-O-CFCF3CF2- OCF2CF2SO2F copolymer emulsions (solid content 15%) 20kg, mixes under 200rpm rotating speeds, obtains fluoropolymer emulsion mixing Material.Then at a temperature of 35 DEG C, under 150rpm speeds of agitator, wadding is added in fluoropolymer emulsion compound with 10g/min Solidifying agent ferric chloride solution (5wt.%), fluoropolymer emulsion compound breakdown of emulsion forms fluoropolymer and fluoride ion polymerization Compositions crude product.By the centrifugal dehydration under 200rpm rotating speeds of above-mentioned composition crude product, then the deionized water at a temperature of 35 DEG C Washing, then dries at 100 DEG C, obtains composition.
Embodiment 3
By polychlorotrifluoroehomopolymer homopolymer emulsion (solid content 25%) 35kg, CTFE and CF2=CF-O- CFCF3CF2-OCF2CF2SO2F copolymer emulsions (solid content 20%) 15kg, mixes under 300rpm rotating speeds, obtains fluoropolymer Emulsion compound.Then at a temperature of 45 DEG C, under 200rpm speeds of agitator, with 12g/min to fluoropolymer emulsion compound It is middle addition flocculant copperas solution (7.5wt.%), fluoropolymer emulsion compound breakdown of emulsion, formed fluoropolymer and Fluorine-containing ionic polymer composition crude product.By the centrifugal dehydration under 300rpm rotating speeds of above-mentioned composition crude product, then in 45 DEG C of temperature Under be washed with deionized, then at 110 DEG C dry, obtain composition.
Embodiment 4
By tetrafluoroethene and hexafluoropropylene copolymer emulsion (solid content 30%) 40kg, vinylidene and CF2=CF-O- CF2CF2SO2F copolymer emulsions (solid content 25%) 10kg, mixes under 150rpm rotating speeds, obtains fluoropolymer emulsion mixing Material.Then at a temperature of 55 DEG C, under 150rpm speeds of agitator, wadding is added in fluoropolymer emulsion compound with 15g/min Solidifying agent calcium chloride solution (10wt.%), fluoropolymer emulsion compound breakdown of emulsion forms fluoropolymer and fluoride ion polymerization Compositions crude product.By the centrifugal dehydration under 100rpm rotating speeds of above-mentioned composition crude product, then the deionized water at a temperature of 55 DEG C Washing, then dries at 120 DEG C, obtains composition.
Embodiment 5
By tetrafluoroethene and ethylene copolymer emulsion (solid content 15%) 42kg, tetrafluoroethene and CF2=CF-O- CF2CF2SO2F copolymer emulsions (solid content 30%) 8kg, mixes under 200rpm rotating speeds, obtains fluoropolymer emulsion compound. Then at a temperature of 65 DEG C, under 150rpm speeds of agitator, flocculant is added in fluoropolymer emulsion compound with 10g/min Copperas solution (2.5wt.%), fluoropolymer emulsion compound breakdown of emulsion forms fluoropolymer and fluoride ion polymerization Compositions crude product.By the centrifugal dehydration under 200rpm rotating speeds of above-mentioned composition crude product, then the deionized water at a temperature of 65 DEG C Washing, then dries at 130 DEG C, obtains composition.
Embodiment 6
By vinylidene and hexafluoropropylene copolymer emulsion (solid content 15%) 27.5kg, CTFE and CF2=CF- O-CF2CF2SO2F copolymer emulsions (solid content 20%) 22.5kg, mixes under 200rpm rotating speeds, obtains fluoropolymer emulsion and mixes Close material.Then at a temperature of 75 DEG C, under 200rpm speeds of agitator, added in fluoropolymer emulsion compound with 12g/min Flocculant aluminum sulfate solution (5wt.%), fluoropolymer emulsion compound breakdown of emulsion, forms fluoropolymer and fluoride ion is poly- Polymer composition crude product.By the centrifugal dehydration under 200rpm rotating speeds of above-mentioned composition crude product, then deionization is used at a temperature of 80 DEG C Water washing, then dries at 140 DEG C, obtains composition.
Embodiment 7
By tetrafluoroethene and perfluoro propyl vinyl ether copolymer emulsion (solid content 20%) 32.5kg, CTFE and CF2=CF-O-CFCF3CF2-OCF2CF2CF2SO2F copolymer emulsions (solid content 25%) 17.5kg, mixes under 300rpm rotating speeds, Obtain fluoropolymer emulsion compound.Then at a temperature of 80 DEG C, under 100rpm speeds of agitator, gathered to fluorine-containing with 15g/min Flocculant ferric chloride solution (7.5wt.%), fluoropolymer emulsion compound breakdown of emulsion is added to be formed in compound emulsion compound Fluoropolymer and fluorine-containing ionic polymer composition crude product.By the centrifugal dehydration under 100rpm rotating speeds of above-mentioned composition crude product, It is washed with deionized at a temperature of 25 DEG C again, then dries at 120 DEG C, obtains composition.
Embodiment 8
By CTFE and ethylene copolymer emulsion (solid content 25%) 37.5kg, tetrafluoroethene and CF2=CF-O- CFCF3CF2-OCF2CF2CF2SO2F copolymer emulsions (solid content 30%) 12.5kg, mixes under 250rpm rotating speeds, obtains fluorine-containing poly- Compound emulsion compound.Then at a temperature of 55 DEG C, under 200rpm speeds of agitator, mixed to fluoropolymer emulsion with 5g/min In material add flocculant copperas solution (10wt.%), fluoropolymer emulsion compound breakdown of emulsion, formed fluoropolymer and Fluorine-containing ionic polymer composition crude product.By the centrifugal dehydration under 250rpm rotating speeds of above-mentioned composition crude product, then in 65 DEG C of temperature Under be washed with deionized, then at 130 DEG C dry, obtain composition.
Embodiment 9
By tetrafluoroethene and perfluoroethylvinyl ether copolymer emulsion (solid content 30%) 25kg, vinylidene and CF2 =CF-O-CFCF3CF2-OCF2CF2CF2SO2F copolymer emulsions (solid content 25%) 25kg, mixes under 150rpm rotating speeds, obtains Fluoropolymer emulsion compound.Then at a temperature of 65 DEG C, under 150rpm speeds of agitator, with 15g/min to fluoropolymer Flocculant calcium chloride solution (5wt.%), fluoropolymer emulsion compound breakdown of emulsion is added to form fluorine-containing poly- in emulsion compound Compound and fluorine-containing ionic polymer composition crude product.By the centrifugal dehydration under 100rpm rotating speeds of above-mentioned composition crude product, then 75 It is washed with deionized at a temperature of DEG C, then dries at 140 DEG C, obtains composition.
Embodiment 10
By tetrafluoroethene and perfluoro methyl vinyl ether copolymer emulsion (solid content 15%) 42kg, vinylidene and CF2 =CF-O-CFCF3CF2-OCF2CF2SO2NCH3Copolymer emulsion (solid content 10%) 8kg, mixes under 200rpm rotating speeds, is contained Fluoropolymer emulsions compound.Then at a temperature of 65 DEG C, under 150rpm speeds of agitator, with 5g/min to fluoropolymer emulsion Flocculant copperas solution (7.5wt.%), fluoropolymer emulsion compound breakdown of emulsion is added to form fluorine-containing poly- in compound Compound and fluorine-containing ionic polymer composition crude product.By the centrifugal dehydration under 200rpm rotating speeds of above-mentioned composition crude product, then 65 It is washed with deionized at a temperature of DEG C, then dries at 130 DEG C, obtains composition.
Properties of product are tested, and the composition product that embodiment 1～10 is obtained is obtained membrane material, film by solution casting method Material tests mechanical property and proton conductivity after alkali/acid conversion, produces without phenomenon of phase separation in membrane material.
Tensile strength test is performed by ASTMD882.
GB/T 20042.3-2009 execution is pressed in proton conductivity test.
Composition masking performance contrast table

Claims (3)

1. a kind of preparation method of fluoride ion membrane material composition, it is characterised in that comprise the following steps：
(a) by weight, by 50～84 parts of fluoropolymer emulsion, fluorine-containing ionic polymer emulsion 16-50 part, 100～ Mix under 300rpm speeds of agitator, obtain fluoropolymer emulsion compound；Described fluoropolymer emulsion is polyvinylidene fluoride Polyamino alkenyl thing emulsion, polytetrafluoroethylene (PTFE) homopolymer emulsion, polychlorotrifluoroehomopolymer homopolymer emulsion, tetrafluoroethene and hexafluoropropene are total to Copolymer emulsion, tetrafluoroethene and ethylene copolymer emulsion, vinylidene and hexafluoropropylene copolymer emulsion, tetrafluoroethene and perfluor Propyl vinyl ether copolymer emulsion, CTFE and ethylene copolymer emulsion, tetrafluoroethene and perfluoroethylvinyl ether One kind in copolymer emulsion, tetrafluoroethene and perfluoro methyl vinyl ether copolymer emulsion, described fluorine-containing ionic polymer Emulsion is vinylidene and CF2=CF-O-CFCF3CF2-OCF2CF2SO2F copolymer emulsions, tetrafluoroethene and CF2=CF-O- CFCF3CF2-OCF2CF2SO2F copolymer emulsions, CTFE and CF2=CF-O-CFCF3CF2-OCF2CF2SO2F copolymers breast Liquid, vinylidene and CF2=CF-O-CF2CF2SO2F copolymer emulsions, tetrafluoroethene and CF2=CF-O-CF2CF2SO2F copolymers Emulsion, CTFE and CF2=CF-O-CF2CF2SO2F copolymer emulsions, CTFE and CF2=CF-O-CFCF3CF2- OCF2CF2CF2SO2F copolymer emulsions, tetrafluoroethene and CF2=CF-O-CFCF3CF2-OCF2CF2CF2SO2F copolymer emulsions, partially PVF and CF2=CF-O-CFCF3CF2-OCF2CF2CF2SO2F copolymer emulsions, vinylidene and CF2=CF-O- CFCF3CF2-OCF2CF2SO2NCH3One kind in copolymer emulsion；
B (), in 25～80 DEG C of temperature, under 100～200rpm speeds of agitator, the fluoropolymer emulsion obtained to step (a) mixes Flocculant solution, fluoropolymer emulsion compound breakdown of emulsion is added to form fluoropolymer and fluorine-containing ionic polymer group in material Compound crude product, described flocculant solution is aluminum sulfate aqueous solution, ferric chloride in aqueous solution, ferrous sulfate aqueous solution, calcium chloride water One kind in solution, the concentration of described flocculant solution is 2.5wt.%～10wt.%, the addition of described flocculant solution Speed is 5g/min～15g/min；
C composition crude product that () obtains step (b) with rotating speed 100～300rpm centrifugal dehydrations, 25～80 DEG C of temperature washes, Dried with 80～150 DEG C of temperature, obtain product.
2. the preparation method of fluoride ion membrane material composition according to claim 1, it is characterised in that described contains The solid content of fluoropolymer emulsions is 15～30wt%.
3. the preparation method of fluoride ion membrane material composition according to claim 1, it is characterised in that described contains Fluorine ion polymer emulsion solid content is 10～30wt.%.
CN201510124244.5A 2015-03-20 2015-03-20 Preparation method of composition for fluorine-containing ion membrane material Active CN104752664B (en)

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