CN108003375A - Preparation method of polyimide diaphragm of high air penetrability and products thereof - Google Patents
Preparation method of polyimide diaphragm of high air penetrability and products thereof Download PDFInfo
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- CN108003375A CN108003375A CN201711442800.9A CN201711442800A CN108003375A CN 108003375 A CN108003375 A CN 108003375A CN 201711442800 A CN201711442800 A CN 201711442800A CN 108003375 A CN108003375 A CN 108003375A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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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
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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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/044—Elimination of an inorganic solid phase
- C08J2201/0444—Salts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- 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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Abstract
The present invention relates to a kind of preparation method of polyimide diaphragm of high air penetrability and products thereof, the inorganic salts pore former for heating the decomposition that can gasify is scattered in solvent at low temperature dispersion liquid is made；Diamines is dissolved in dispersion liquid, dianhydride is added after two amine solvents, the polyamic acid solution containing pore former is made, dianhydride and diamines molar ratio are 0.98:1~1.02:1, on the basis of polyamic acid and solvent gross mass, polyamide acid content is 12% ~ 25%, and solvent content is 75% ~ 88%, and on the basis of the gross mass of polyamic acid, porogen content is 20% ~ 35%；By polyamic acid solution, plastic film mulch, heating make solvent volatilize to obtain gel or self-supporting state film on a glass, and heating makes pore former be made film pore-forming by thermal decomposition；Biaxial tension will be carried out after being preheated at high temperature into pore membrane, rupture film surface compacted zone, continue high temperature imidization, porous polyimide diaphragm is obtained, the present invention is cost-effective, and production efficiency is high, control solvent residues amount in film, the porosity of film is improved 60%, obtain the membrane of more large aperture and porosity, drawn metacneme surface dense layer is opened.
Description
Technical field
The present invention relates to a kind of battery diaphragm, and in particular to a kind of cost is low, the polyimides of efficient high air penetrability
Preparation method of membrane and products thereof.
Background technology
Membrane is the important component of lithium ion battery, its act on mainly isolation positive and negative electrode, make in electrolyte from
Son passes through between positive and negative anodes and limits electronics and pass freely through.In addition, membrane also has a major impact the security of battery.
Battery is in the case of improper use, and when inside battery or outside overheat, traditional polyalkene diaphragm is in battery temperature more than 160
DEG C when can fuse, cause positive and negative anodes contact and it is short-circuit, so as to cause batteries caught fire or explosion, seriously jeopardize the life of user
Safety.
Polyimides is a kind of good insulating materials of comprehensive performance, has excellent heat endurance and mechanical performance, its
Long-time service temperature may be up to more than 300 DEG C, be preferable battery diaphragm material.The system of polyimide battery membrane is prepared at present
Preparation Method has method of electrostatic spinning, phase inversion method and an inorganic filler removal method, the prior art there are it is certain the drawbacks of, such as electrostatic
Spin processes, low production efficiency, equipment cost is high, complex process etc., can be used during phase inversion method and the preparation of inorganic filler method
Coagulator, inorganic filler remover etc., coagulator and inorganic filler compared with the preparation method of common polyimides imines membrane
The use of remover etc. also have impact on the production efficiency of polyimide diaphragm.
As disclosed a kind of preparation method of polyimide diaphragm, this method in Chinese invention patent CN 1,023 54733
It is middle by the use of inorganic matters such as lithias as pore former, lithia is dispersed in polyamic acid solution, is contained after plastic film mulch imidization
There is the Kapton of lithia, then clean removing lithia repeatedly with dilute hydrochloric acid and obtain porous polyimide diaphragm.
This method obtains after Kapton, it is necessary to the last handling process of multistep, adds time cost, has seriously affected membrane
Production efficiency.
The content of the invention
There is provided a kind of without being used after imidization it is an object of the invention to overcome the deficiencies in the prior art
Reagent removes inorganic filler and preparation method of polyimide diaphragm of high air penetrability of cleaning step repeatedly and products thereof, makes
By the use of the filler that high temperature can be gasified totally as pore former, decomposed under polyimides acid gel or self-supporting state, in nearly solid-state
Under state, the polyimide diaphragm of the aperture bigger than filler particle diameter itself and high porosity is made by gas expansion, by into
Once step stretching so that surface dense layer is opened, and then the gas permeability of increment rate membrane.
The object of the present invention is achieved like this：
A kind of preparation method of the polyimide diaphragm of high air penetrability, it is characterised in that the system for preparing polyimide diaphragm
Preparation Method comprises the following steps：
Step 1）, the inorganic salts pore former of decomposition of being gasified totally will be heated be scattered at low temperature in solvent, be made scattered
Liquid A；
Step 2）, diamines is dissolved in above-mentioned dispersion liquid A, after two amine solvents, be slowly added to dianhydride, when stirring 2 ~ 4 is small after, system
The polyamic acid solution containing pore former is obtained, wherein the molar ratio of the dianhydride and diamines is 0.98:1~1.02:1, with polyamide
On the basis of the gross mass of acid and solvent, the content of the polyamic acid is 12% ~ 25%, and the content of the solvent is 75% ~ 88%, with
On the basis of the gross mass of polyamic acid, the content of the pore former is 20% ~ 35%；
Step 3）, by above-mentioned polyamic acid solution plastic film mulch on a glass, solvent content is volatilized by heating, coagulated
The film of glue or self-supporting state, further heating make pore former be made film pore-forming by thermal decomposition；
Step 4）, by the film of pore-forming, carry out biaxial tension after preheating at high temperature, the compacted zone of film surface rupture, continue height
Warm imidization, obtains porous polyimide diaphragm.
The pore former is selected from ammonium oxalate, ammonium chloride, ammonium carbonate, ammonium hydrogen carbonate, ammonium nitrate, inferior ammonium nitrate, ammonium ceric nitrate
In one or more of any combinations, the decomposition gasification temperature of the pore former is less than 400 DEG C, and the pore former is averaged
Particle diameter is 0.03 ~ 1 micron.
The diamines is the monomer of common synthesis of polyimides, including 4,4 '-diaminodiphenyl ether, 3, and 4 '-diaminourea
Diphenyl ether, p-phenylenediamine, m-phenylene diamine (MPD), 5,4 '-diaminourea -2- phenyl benzoxazoles, 2-（4- aminophenyls）- 5 amino benzos
One or more of any ratios in imidazoles, 4,4'- diaminourea -2,2'- dimethyl -1,1'- biphenyl, 4,4 '-benzidine
Combination.
The dianhydride is the monomer of common synthesis of polyimides, including pyromellitic dianhydride, 3,3 ', 4,4 '-biphenyl four
One kind in formic acid dianhydride, 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride (BTDA), Bisphenol A Type Diether Dianhydride or
Several any combinations.
The solvent is the solvent that can dissolve polyamic acid, is specially n,N-dimethylacetamide（DMAc）, N, N- bis-
Methylformamide（DMF）, 1-methyl-2-pyrrolidinone, any of the mixed solvent of methanol and tetrahydrofuran, when with methanol and
When the mixed solvent of tetrahydrofuran is solvent, on the basis of the gross mass of methanol and tetrahydrofuran, the content of tetrahydrofuran used
For 70% ~ 80%, the content of methanol used is 20% ~ 30%.
In step 1）Described in inorganic salts pore former be scattered at low temperature in solvent, the low temperature dispersion temperature be -5 ~ 30
℃。
The heat treatment process for making solvent content volatilize is specially when processing 1.5 ~ 3 is small at a temperature of 70 ~ 90 DEG C；It is described
Make the heat treatment process that pore former is thermally decomposed to be handled 5 ~ 30 minutes at a temperature of 90 ~ 100 DEG C.
In step 4）In, the preheating temperature of the biaxial tension is 150 ~ 180 DEG C, and the preheating time is 60 ~ 120s, institute
It is bidirectional static stretching-machine to state biaxial tension device therefor, and the stretching mode of the biaxial tension stretches for bi-directional synchronization, described
The draft temperature of biaxial tension is 150 ~ 180 DEG C, and the draw ratio of the longitudinal stretching of the biaxial tension is 1:1.1~1:1.15 institute
The cross directional stretch ratio for stating biaxial tension is 1:1.1~1:1.2, film is put into baking oven the imidization that progressively heats up afterwards, is obtained porous
Polyimide diaphragm.
A kind of a kind of polyimide diaphragm of high air penetrability, it is characterised in that polyimide diaphragm of high air penetrability
It is to be prepared using a kind of preparation method of the polyimide diaphragm of any of the above-described high air penetrability.
Compared with prior art, the method have the characteristics that：
1st, the pore former that the present invention uses is the labile material that is heated, which can decompose completely within 400 DEG C, its is anti-
The all gas of product is answered, the excess step for the filler that comes in and goes out compared with prior art without using unnecessary solvent is cost-effective,
It is beneficial to improve production efficiency.
2nd, the present invention, by controlling the residual volume of solvent in film, can make the porosity of film under same formula
Improve 60%.
3rd, during pore former decomposition gasification of the present invention, polyamic acid is in the state of a kind of gel or self-supporting, still not at
The state being fully cured, pore former decompose the gas expansion produced, make hole aperture increases, porosity increase, with using traditional nothing
Machine filler pore former is compared, and can obtain the aperture of bigger and the membrane of porosity.
4th, the membrane after stretched, surface dense layer are opened, can be made Gurley values be 5 ~ 230s/100ml every
Film.
Embodiment
With reference to specific embodiment, the invention will be further described, to be better understood from present disclosure, but this
Invention is not limited to following embodiments.
Embodiment 1：Weigh (the NH that 11.25g average grain diameters are 0.05 micron4)2C2O4It is scattered in 255gN, N- dimethyl
It is spare in acetamide solution, the 4 of 21.54g is then weighed, 4 '-diaminodiphenyl ether（ODA）Add in above-mentioned solvent, treat diamines
After dissolving, by the pyromellitic dianhydride of 23.46g（PMDA）Substep is added in above-mentioned solvent, when stirring 2 is small, after vacuum outgas, is obtained
To polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, when 70 DEG C of processing 2.5 are small, 90 DEG C of processing 5
Minute, 95 DEG C are handled 10 minutes, and 100 DEG C of processing after ten minutes, be able to will be placed in the polyimide film of the non-imidization of self-supporting
In static stretch machine, progress bi-directional synchronization stretching, wherein 1.1 times of longitudinal stretching after 150 DEG C of preheating 120s, 1.1 times of cross directional stretch,
Then film is placed in baking oven after progressively heating carries out imidization and obtains aperture 0.11, porosity 52.3%, Gurley values are 93s/
The polyimide diaphragm of 100ml.
Embodiment 2：Weigh (the NH that 11.25g average grain diameters are 0.05 micron4)2C2O4It is scattered in 255gN, N- dimethyl
It is spare in acetamide solution, the 4 of 21.54g is then weighed, 4 '-diaminodiphenyl ether（ODA）Add in above-mentioned solvent, treat diamines
After dissolving, by the pyromellitic dianhydride of 23.46g（PMDA）Substep is added in above-mentioned solvent, when stirring 2 is small, after vacuum outgas, is obtained
To polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, when 70 DEG C of processing 2.5 are small, 90 DEG C of processing 5
Minute, 95 DEG C are handled 10 minutes, and 100 DEG C of processing after ten minutes, be able to will be placed in the polyimide film of the non-imidization of self-supporting
In static stretch machine, bi-directional synchronization stretching, wherein 1.1 times of longitudinal stretching, cross directional stretch 1.15 are carried out after 160 DEG C of preheating 100s
Times, then film is placed in baking oven after progressively heating carries out imidization and obtains aperture 0.11, porosity 53.5%, Gurley values are
The polyimide diaphragm of 87s/100ml.
Embodiment 3：Weigh (the NH that 11.25g average grain diameters are 0.05 micron4)2C2O4It is scattered in 255gN, N- dimethyl
It is spare in acetamide solution, the 4 of 21.54g is then weighed, 4 '-diaminodiphenyl ether（ODA）Add in above-mentioned solvent, treat diamines
After dissolving, by the pyromellitic dianhydride of 23.46g（PMDA）Substep is added in above-mentioned solvent, when stirring 2 is small, after vacuum outgas, is obtained
To polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, when 70 DEG C of processing 2.5 are small, 90 DEG C of processing 5
Minute, 95 DEG C are handled 10 minutes, and 100 DEG C of processing after ten minutes, be able to will be placed in the polyimide film of the non-imidization of self-supporting
In static stretch machine, bi-directional synchronization stretching, wherein 1.15 times of longitudinal stretching, cross directional stretch 1.15 are carried out after 170 DEG C of preheating 80s
Times, then film is placed in baking oven after progressively heating carries out imidization and obtains aperture 0.12, porosity 54.6%, Gurley values are
The polyimide diaphragm of 70s/100ml.
Embodiment 4：Weigh (the NH that 11.25g average grain diameters are 0.05 micron4)2C2O4It is scattered in 255gN, N- dimethyl
It is spare in acetamide solution, the 4 of 21.54g is then weighed, 4 '-diaminodiphenyl ether（ODA）Add in above-mentioned solvent, treat diamines
After dissolving, by the pyromellitic dianhydride of 23.46g（PMDA）Substep is added in above-mentioned solvent, when stirring 2 is small, after vacuum outgas, is obtained
To polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, when 70 DEG C of processing 2.5 are small, 90 DEG C of processing 5
Minute, 95 DEG C are handled 10 minutes, and 100 DEG C of processing after ten minutes, be able to will be placed in the polyimide film of the non-imidization of self-supporting
In static stretch machine, progress bi-directional synchronization stretching, wherein 1.15 times of longitudinal stretching after 180 DEG C of preheating 60s, 1.2 times of cross directional stretch,
Then film is placed in baking oven after progressively heating carries out imidization and obtains aperture 0.12, porosity 55.7%, Gurley values are 60s/
The polyimide diaphragm of 100ml.
Embodiment 5：Weigh (the NH that 11.25g average grain diameters are 0.05 micron4)2C2O4It is scattered in 255gN, N- dimethyl
It is spare in acetamide solution, the 4 of 21.54g is then weighed, 4 '-diaminodiphenyl ether（ODA）Add in above-mentioned solvent, treat diamines
After dissolving, by the pyromellitic dianhydride of 23.46g（PMDA）Substep is added in above-mentioned solvent, when stirring 2 is small, after vacuum outgas, is obtained
To polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, when 70 DEG C of processing 4 are small, 90 DEG C of processing 20
Minute, 95 DEG C are handled 20 minutes, after 100 DEG C are handled 30 minutes, be able to will be placed in the polyimide film of the non-imidization of self-supporting
In static stretch machine, bi-directional synchronization stretching, wherein 1.12 times of longitudinal stretching, cross directional stretch 1.15 are carried out after 170 DEG C of preheating 80s
Times, then film is placed in baking oven after progressively heating carries out imidization and obtains aperture 0.086, porosity 38.4%, Gurley values are
The polyimide diaphragm of 230s/100ml.
Embodiment 6：Weigh (the NH that 13.5g average grain diameters are 0.05 micron4)2C2O4It is scattered in 255gN, N- dimethyl second
It is spare in amide solution, the 4 of 21.54g is then weighed, 4 '-diaminodiphenyl ether（ODA）Add in above-mentioned solvent, treat that diamines is molten
Xie Hou, by the pyromellitic dianhydride of 23.46g（PMDA）Substep is added in above-mentioned solvent, when stirring 2 is small, after vacuum outgas, is obtained
Polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, when 70 DEG C of processing 4 are small, 90 DEG C of processing 20
Minute, 95 DEG C are handled 20 minutes, after 100 DEG C are handled 30 minutes, be able to will be placed in the polyimide film of the non-imidization of self-supporting
In static stretch machine, bi-directional synchronization stretching, wherein 1.13 times of longitudinal stretching, cross directional stretch 1.15 are carried out after 170 DEG C of preheating 80s
Times, then film is placed in baking oven after progressively heating carries out imidization and obtains aperture 0.090, porosity 47.2%, Gurley values are
The polyimide diaphragm of 160s/100ml.
Embodiment 7：Weigh (the NH that 15.75g average grain diameters are 0.05 micron4)2C2O4It is scattered in 255gN, N- dimethyl
It is spare in acetamide solution, the 4 of 21.54g is then weighed, 4 '-diaminodiphenyl ether（ODA）Add in above-mentioned solvent, treat diamines
After dissolving, by the pyromellitic dianhydride of 23.46g（PMDA）Substep is added in above-mentioned solvent, when stirring 2 is small, after vacuum outgas, is obtained
To polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, when 70 DEG C of processing 2.5 are small, 90 DEG C of processing
2.5 minutes, 95 DEG C handle 20 minutes, 100 DEG C processing 30 minutes after, by can with the polyimide film of the non-imidization of self-supporting,
It is placed in static stretch machine, bi-directional synchronization stretching, wherein 1.1 times of longitudinal stretching, cross directional stretch is carried out after 180 DEG C of preheating 100s
1.1 times, then film is placed in baking oven after progressively heating carries out imidization and obtains aperture 0.071, porosity 48%, Gurley values
For the polyimide diaphragm of 153s/100ml.
Embodiment 8：Weigh (the NH that 15.75g average grain diameters are 0.05 micron4)2C2O4It is scattered in 255gN, N- dimethyl
It is spare in acetamide solution, the 4 of 21.54g is then weighed, 4 '-diaminodiphenyl ether（ODA）Add in above-mentioned solvent, treat diamines
After dissolving, by the pyromellitic dianhydride of 23.46g（PMDA）Substep is added in above-mentioned solvent, when stirring 2 is small, after vacuum outgas, is obtained
To polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, when 90 DEG C of processing 1.5 are small, 95 DEG C of processing
20 minutes, after 100 DEG C are handled 30 minutes, it be able to will be placed in the polyimide film of the non-imidization of self-supporting in static stretch machine,
Bi-directional synchronization stretching, wherein 1.15 times of longitudinal stretching are carried out after 170 DEG C of preheating 100s, film, is then placed in by 1.1 times of cross directional stretch
Progressively heating obtains aperture 0.11, porosity 73.4% after carrying out imidization in baking oven, and the polyamides that Gurley values are 8s/100ml is sub-
Amine membrane.
Embodiment 9：Weigh (the NH that 15.75g average grain diameters are 0.05 micron4)2C2O4It is scattered in 255gN, N- dimethyl
It is spare in formamide solution, the 4 of 21.31g is then weighed, 4 '-diaminodiphenyl ether（ODA）Add in above-mentioned solvent, treat diamines
After dissolving, by the pyromellitic dianhydride of 23.69g（PMDA）Substep is added in above-mentioned solvent, when stirring 2 is small, after vacuum outgas, is obtained
To polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, when 90 DEG C of processing 1.5 are small, 95 DEG C of processing
20 minutes, after 100 DEG C are handled 30 minutes, it be able to will be placed in the polyimide film of the non-imidization of self-supporting in static stretch machine,
Bi-directional synchronization stretching, wherein 1.15 times of longitudinal stretching are carried out after 170 DEG C of preheating 100s, film, is then placed in by 1.1 times of cross directional stretch
Progressively heating obtains aperture 0.11, porosity 68.4% after carrying out imidization in baking oven, and Gurley values are the polyamides of 32s/100ml
Imines membrane.
Embodiment 10：Weigh (the NH that 7.2g average grain diameters are 0.04 micron4)2C2O4It is scattered in 264gN, N- dimethyl methyls
It is spare in amide solution, the 4 of 17.05g is then weighed, 4 '-diaminodiphenyl ether（ODA）Add in above-mentioned solvent, treat that diamines is molten
Xie Hou, by the pyromellitic dianhydride of 18.95g（PMDA）Substep is added in above-mentioned solvent, when stirring 4 is small, after vacuum outgas, is obtained
Polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, when 80 DEG C of processing 2 are small, 95 DEG C of processing 20
Minute, after 100 DEG C are handled 30 minutes, it be able to will be placed in the polyimide film of the non-imidization of self-supporting in static stretch machine,
Bi-directional synchronization stretching, wherein 1.12 times of longitudinal stretching are carried out after 170 DEG C of preheating 100s, film, is then placed in by 1.1 times of cross directional stretch
Progressively heating obtains aperture 0.05, porosity 45.3% after carrying out imidization in baking oven, and Gurley values are the polyamides of 180s/100ml
Imines membrane.
Embodiment 11：Weigh (the NH that 7.5g average grain diameters are 0.06 micron4)2C2O4It is micro- for 0.06 with 7.5g average grain diameters
The NH4NO3 of rice is scattered in spare in 240gN-methylpyrrolidone solution, then weighs the 4 of 28.72g, 4 '-diaminourea hexichol
Ether（ODA）Add in above-mentioned solvent, after two amine solvents, by the pyromellitic dianhydride of 31.28g（PMDA）Substep adds above-mentioned molten
In agent, when stirring 2.5 is small, after vacuum outgas, polyamic acid solution is obtained.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, when 70 DEG C of processing 3 are small, 90 DEG C of processing 3 are small
When, 95 DEG C are handled 20 minutes, after 100 DEG C are handled 30 minutes, be able to will be placed in quiet with the polyimide film of the non-imidization of self-supporting
In state stretching-machine, progress bi-directional synchronization stretching, wherein 1.15 times of longitudinal stretching after 150 DEG C of preheating 80s, 1.12 times of cross directional stretch,
Then film is placed in baking oven after progressively heating carries out imidization and obtains aperture 0.09, porosity 56.9%, Gurley values are 100/
The polyimide diaphragm of 100ml.
Embodiment 12：Weigh (the NH that 7.5g average grain diameters are 0.05 micron4)2C2O4It is micro- for 0.05 with 7.5g average grain diameters
The NH4NO3 of rice is scattered in spare in 225gN-methylpyrrolidone solution, then weighs the 4 of 35.90g, 4 '-diaminourea hexichol
Ether（ODA）Add in above-mentioned solvent, after two amine solvents, by the pyromellitic dianhydride of 39.10g（PMDA）Substep adds above-mentioned molten
In agent, when stirring 3 is small, after vacuum outgas, polyamic acid solution is obtained.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, when 70 DEG C of processing 3 are small, 90 DEG C of processing 3 are small
When, 95 DEG C are handled 20 minutes, after 100 DEG C are handled 30 minutes, be able to will be placed in quiet with the polyimide film of the non-imidization of self-supporting
In state stretching-machine, carry out bi-directional synchronization stretching, wherein 1.15 times of longitudinal stretching, cross directional stretch 1.12 after 150 DEG C of preheating 100s
Times, then film is placed in baking oven after progressively heating carries out imidization and obtains aperture 0.09, porosity 67.8%, Gurley values are
The polyimide diaphragm of 25/100ml.
Comparative example 1：Weigh (the NH that 11.25g average grain diameters are 0.05 micron4)2C2O4It is scattered in 255gN, N- dimethyl
It is spare in acetamide solution, the 4 of 21.54g is then weighed, 4 '-diaminodiphenyl ether（ODA）Add in above-mentioned solvent, treat diamines
After dissolving, by the pyromellitic dianhydride of 23.46g（PMDA）Substep is added in above-mentioned solvent, when stirring 2 is small, after vacuum outgas, is obtained
To polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, when 70 DEG C of processing 2.5 are small, 90 DEG C of processing 5
Minute, 95 DEG C are handled 10 minutes, and 100 DEG C of processing after ten minutes, continue progressively heating and carry out after imidization that to obtain aperture 0.11 micro-
Rice, porosity 51.33%, Gurley values are the polyimide diaphragm of 230s/100ml
Comparative example 2：The aluminium oxide that 11.25g average grain diameters are 0.05 micron is uniformly dispersed in N ' the N- dimethyl second of 255g
In amide solvent, the 4 of 21.54g is added into solvent, 4 '-diaminodiphenyl ether（ODA）, after and after amine solvent, by 23.46g's
Pyromellitic dianhydride（PMDA）Substep is added in above-mentioned solvent, when stirring 3 is small in the environment less than 30 DEG C, after vacuum outgas,
Obtain polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, it is thin progressively polyimides to be obtained after imidization in an oven
Film.Above-mentioned film is extracted repeatedly with dilute hydrochloric acid solution, aluminium oxide is removed, is then cleaned with distilled water to neutrality, and place baking
Case is dried, and obtains 0.05 micron of aperture, porosity 25%, and Gurley values are the porous polyimide diaphragm of 780s/100ml.
Claims (9)
- A kind of 1. preparation method of the polyimide diaphragm of high air penetrability, it is characterised in that the polyimide diaphragm for preparing Preparation method comprises the following steps：Step 1）, the inorganic salts pore former of decomposition of being gasified totally will be heated be scattered at low temperature in solvent, be made scattered Liquid A；Step 2）, diamines is dissolved in above-mentioned dispersion liquid A, after two amine solvents, be slowly added to dianhydride, when stirring 2 ~ 4 is small after, system The polyamic acid solution containing pore former is obtained, wherein the molar ratio of the dianhydride and diamines is 0.98:1~1.02:1, with polyamide On the basis of the gross mass of acid and solvent, the content of the polyamic acid is 12% ~ 25%, and the content of the solvent is 75% ~ 88%, with On the basis of the gross mass of polyamic acid, the content of the pore former is 20% ~ 35%；Step 3）, by above-mentioned polyamic acid solution plastic film mulch on a glass, solvent content is volatilized by heating, coagulated The film of glue or self-supporting state, further heating make pore former be made film pore-forming by thermal decomposition；Step 4）, by the film of pore-forming, carry out biaxial tension after preheating at high temperature, the compacted zone of film surface rupture, continue height Warm imidization, obtains porous polyimide diaphragm.
- 2. the preparation method of the polyimide diaphragm of a kind of high air penetrability according to claim 1, it is characterised in that described The one kind or several of pore former in ammonium oxalate, ammonium chloride, ammonium carbonate, ammonium hydrogen carbonate, ammonium nitrate, inferior ammonium nitrate, ammonium ceric nitrate Any combination of kind, the decomposition gasification temperature of the pore former are less than 400 DEG C, and the average grain diameter of the pore former is 0.03 ~ 1 Micron.
- 3. the preparation method of the polyimide diaphragm of a kind of high air penetrability according to claim 1, it is characterised in that described Diamines is the monomer of common synthesis of polyimides, including 4,4 '-diaminodiphenyl ether, 3, and 4 '-diaminodiphenyl ether, to benzene two Amine, m-phenylene diamine (MPD), 5,4 '-diaminourea -2- phenyl benzoxazoles, 2-（4- aminophenyls）- 5 aminobenzimidazoles, 4,4'- diaminos One or more of any combinations in base -2,2'- dimethyl -1,1'- biphenyl, 4,4 '-benzidine.
- 4. the preparation method of the polyimide diaphragm of a kind of high air penetrability according to claim 1, it is characterised in that described Dianhydride is the monomer of common synthesis of polyimides, including pyromellitic dianhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 2, It is one or more of any in 2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride (BTDA), Bisphenol A Type Diether Dianhydride Than combination.
- 5. the preparation method of the polyimide diaphragm of a kind of high air penetrability according to claim 1, it is characterised in that described Solvent is the solvent that can dissolve polyamic acid, is specially n,N-dimethylacetamide（DMAc）, N,N-dimethylformamide （DMF）, 1-methyl-2-pyrrolidinone, any of the mixed solvent of methanol and tetrahydrofuran, when with methanol and tetrahydrofuran When mixed solvent is solvent, on the basis of the gross mass of methanol and tetrahydrofuran, the content of tetrahydrofuran used is 70% ~ 80%, The content of methanol used is 20% ~ 30%.
- 6. the preparation method of the polyimide diaphragm of a kind of high air penetrability according to claim 1, it is characterised in that in step Rapid 1）Described in inorganic salts pore former be scattered at low temperature in solvent, the low temperature dispersion temperature be -5 ~ 30 DEG C.
- 7. the preparation method of the polyimide diaphragm of a kind of high air penetrability according to claim 1, it is characterised in that described It is specially when processing 1.5 ~ 3 is small at a temperature of 70 ~ 90 DEG C to make the heat treatment process that solvent content volatilizees；It is described pore former is heated The heat treatment process of decomposition is to be handled 5 ~ 30 minutes at a temperature of 90 ~ 100 DEG C.
- 8. the preparation method of the polyimide diaphragm of a kind of high air penetrability according to claim 1, it is characterised in that in step Rapid 4）In, the preheating temperature of the biaxial tension is 150 ~ 180 DEG C, and the preheating time is 60 ~ 120s, the biaxial tension institute It is bidirectional static stretching-machine with equipment, the stretching mode of the biaxial tension stretches for bi-directional synchronization, the drawing of the biaxial tension Temperature is stretched for 150 ~ 180 DEG C, and the draw ratio of the longitudinal stretching of the biaxial tension is 1:1.1~1:1.15, the biaxial tension Cross directional stretch ratio is 1:1.1~1:1.2, film is put into baking oven the imidization that progressively heats up afterwards, obtain porous polyimides every Film.
- 9. a kind of polyimide diaphragm of high air penetrability, it is characterised in that a kind of polyimide diaphragm of high air penetrability is Prepared using a kind of preparation method of the polyimide diaphragm of any high air penetrability of claim 1 ~ 8.
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| CN109280190A (en) * | 2018-08-01 | 2019-01-29 | 乳源东阳光氟树脂有限公司 | A kind of polyimide porous film and preparation method thereof |
| CN111430649A (en) * | 2020-05-08 | 2020-07-17 | 胡欣宇 | Preparation method of lithium ion battery diaphragm and lithium ion battery |
| CN112072048A (en) * | 2020-08-03 | 2020-12-11 | 泰州衡川新能源材料科技有限公司 | Lithium ion battery diaphragm and preparation method thereof |
| CN113234245A (en) * | 2021-06-01 | 2021-08-10 | 桂林电器科学研究院有限公司 | Low-dielectric high-insulation-strength polyimide film and preparation method thereof |
| CN116315447A (en) * | 2023-05-04 | 2023-06-23 | 合肥长阳新能源科技有限公司 | Polyimide porous microsphere coated diaphragm for lithium battery and preparation method thereof |
| WO2023168626A1 (en) * | 2022-03-09 | 2023-09-14 | 江苏矽时代材料科技有限公司 | Separator and method for preparing separator |
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