CN108172740A - High porosity polyimide diaphragm preparation method and products thereof - Google Patents
High porosity polyimide diaphragm preparation method and products thereof Download PDFInfo
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- CN108172740A CN108172740A CN201711442841.8A CN201711442841A CN108172740A CN 108172740 A CN108172740 A CN 108172740A CN 201711442841 A CN201711442841 A CN 201711442841A CN 108172740 A CN108172740 A CN 108172740A
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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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- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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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
- H01M50/463—Separators, membranes or diaphragms characterised by their shape
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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 high porosity polyimide diaphragm preparation method and products thereof, the inorganic salts pore former that heating is capable of to decomposition gasification completely is scattered in solvent at low temperature, and dispersion liquid A is made for this；Porogen content is 2.6% ~ 17.2% on the basis of solvent gross mass；Diamines is dissolved in dispersion liquid A, is slowly added to dianhydride, obtains the polyamic acid solution containing pore former, dianhydride and diamines molar ratio are 0.98:1~1.05:1, on the basis of polyamic acid and solvent gross mass, polyamide acid content is 15% ~ 30%, and solvent content is 70% ~ 85%；By polyamic acid solution plastic film mulch on a glass, being put into heating in baking oven makes solvent volatilize, obtain gel or the film of self-supporting state, continuing heating is thermally decomposed pore former, make film pore-forming, continue heating make film imidization after obtain porous polyimide diaphragm, the cost for preparing polyimide diaphragm is low, efficient.
Description
Technical field
The present invention relates to a kind of battery diaphragms, and in particular to a kind of to prepare polyimide diaphragm using inorganic filler removal method
Cost is low, efficient high porosity polyimide diaphragm preparation method and products thereof.
Background technology
Diaphragm is the important component of lithium ion battery, effect 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 to this, diaphragm also has a major impact the safety of battery.
Battery is in the case of improper use, and when inside battery or outside overheat, traditional polyalkene diaphragm is more than 160 in battery temperature
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 thermal stability and mechanical performance,
Temperature is used for a long time and may be up to 300 DEG C or more, is ideal battery diaphragm material.The system of polyimide battery diaphragm is prepared at present
Preparation Method has method of electrostatic spinning, phase inversion method and inorganic filler removal method, and there are certain drawbacks, such as Static Spinning for the prior art
Silk method, low production efficiency, equipment cost is high, complex process etc., can be used during phase inversion method and the preparation of inorganic filler method solidifying
Gu agent, inorganic filler remover etc., compared with the preparation method of common polyimides imines diaphragm coagulator and inorganic filler go
Except the use of agent etc. also affects the production efficiency of polyimide diaphragm.
If disclosed a kind of preparation method of polyimide diaphragm in Chinese invention patent CN102354733, in this method
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
Then the Kapton of lithia with dilute hydrochloric acid cleans removing lithia and obtains porous polyimide diaphragm repeatedly.It should
After method obtains Kapton, the last handling process of multistep is needed, increases time cost, seriously affected the life of diaphragm
Produce efficiency.
Invention content
It 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 cleaning step repeatedly, porous polyimide diaphragm can be directly obtained after imidization, significantly
High porosity polyimide diaphragm preparation method of polyimide diaphragm production efficiency and products thereof is improved, it can be complete using high temperature
The inorganic filler of gasification is decomposed, high viscous or near solid-state like as pore former under polyimides acid gel or self-supporting state
Under state, by gas expansion, the polyimide diaphragm of the obtained aperture bigger than filler grain size itself and high porosity.
The object of the present invention is achieved like this：
A kind of preparation method of high porosity polyimide diaphragm, which is characterized in that the preparation method includes the following steps：
Step 1）, will heat and be capable of the inorganic salts pore former of decomposition gasification completely and be scattered in solvent at low temperature, be made and disperse
Liquid A；On the basis of the gross mass of solvent, the content of the pore former is 2.6% ~ 17.2%；
Step 2）, diamines is dissolved in above-mentioned dispersion liquid A, be then slowly added into dianhydride, stir 2 ~ 24 hours, obtain containing pore-forming
The polyamic acid solution of agent, wherein the molar ratio of the dianhydride and diamines is 0.98:1~1.05:1, with polyamic acid and solvent
On the basis of gross mass, the content of the polyamic acid is 15% ~ 30%, and the content of the solvent is 70% ~ 85%；
Step 3）, by above-mentioned polyamic acid solution plastic film mulch on a glass, being then placed in heating in baking oven makes solvent portion volatilize,
Gel or the film of self-supporting state are obtained, continuing heating is thermally decomposed pore former, makes film pore-forming, and continuing heating makes film imidization
Porous polyimide diaphragm is obtained afterwards.
In step 1）Described in pore former for ammonium oxalate, ammonium chloride, ammonium carbonate, ammonium hydrogen carbonate, ammonium nitrate, inferior ammonium nitrate,
One or more of combination in ammonium ceric nitrate, the average grain diameter of the pore former is 0.03 ~ 1 micron,
In step 1）Described in low temperature dispersion temperature be -5 ~ 30 DEG C.
The solvent is the solvent that can dissolve polyamic acid, specially n,N-dimethylacetamide（DMAc）, N, N- bis-
Methylformamide（DMF）, methanol and tetrahydrofuran any one of mixed solvent, when molten with the mixing of methanol and tetrahydrofuran
When agent is solvent, on the basis of the gross mass of methanol and tetrahydrofuran, the content of tetrahydrofuran used is 70% ~ 80%, first used
The content of alcohol is 20% ~ 30%.
The decomposition gasification temperature of the pore former is no more than 400 DEG C.
The diamines is the monomer of common synthesis of polyimides, including 4,4 '-diaminodiphenyl ether, 3,4 '-diamino
Diphenyl ether, p-phenylenediamine, m-phenylene diamine (MPD), 5,4 '-diamino -2- phenyl benzoxazoles, 2-（4- aminophenyls）- 5 amino benzos
The arbitrary ratio of one or more of imidazoles, 4,4'- diamino -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, and 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 processing procedure that solvent portion is made to volatilize is handled 1 ~ 5 hour at 60 ~ 90 DEG C, described that pore former is made to be heated
The processing procedure of decomposition is handled 5 ~ 30 minutes at 90 ~ 100 DEG C, and the processing procedure of the imidization is at 150 ~ 300 DEG C
Processing 0.5 ~ 1 hour.
A kind of high porosity polyimide diaphragm, which is characterized in that the high porosity polyimide diaphragm is using upper
State the preparation method preparation of any high porosity polyimide diaphragm.
Compared with prior art, the method have the characteristics that：
1st, the pore former that the present invention uses is the labile inorganic salts that are heated, which can decompose completely within 400 DEG C,
The all gas of reaction product is removed compared with the technology of pore former with existing using inorganic salts without using extra solvent
Pore former improves production efficiency while cost-effective.
2nd, the present invention, by controlling the residual volume of solvent in film, can improve the porosity of film under same formula
62%。
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 generated, make hole aperture increases, porosity increases, with using traditional nothing
Machine filler pore former is compared, and can obtain the aperture of bigger and the diaphragm of porosity.
Specific 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 embodiment.
Embodiment 1:Weigh (the NH that 11.25g average grain diameters are 0.03 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）It adds in above-mentioned solvent, treats diamines
After dissolving, by the pyromellitic dianhydride of 23.46g（PMDA）Substep is added in above-mentioned solvent, and 2 are stirred in the environment less than 30 DEG C
Hour, after vacuum outgas, obtain polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, is handled at 70 DEG C 3 hours, 90 DEG C handle 5 points
Clock, 95 DEG C are handled 10 minutes, and 100 DEG C are handled 10 minutes, and 150 DEG C are handled 30 minutes, and 200 DEG C are handled 30 minutes, 250 DEG C of processing 30
Minute, 300 DEG C are handled 0.5 hour, and it is 0.06 micron that average pore size is obtained after imidization, and porosity is 51.2% polyimides
Diaphragm.
Embodiment 2:Weigh (the NH that 11.25g average grain diameters are 0.03 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）It adds in above-mentioned solvent, treats diamines
After dissolving, by the pyromellitic dianhydride of 23.46g（PMDA）Substep is added in above-mentioned solvent, and 2 are stirred in the environment less than 30 DEG C
Hour, after vacuum outgas, obtain polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, is handled at 60 DEG C 5 hours, 90 DEG C of processing 10
Minute, 95 DEG C are handled 10 minutes, and 100 DEG C are handled 10 minutes, and 150 DEG C are handled 30 minutes, and 200 DEG C are handled 30 minutes, 250 DEG C of processing
30 minutes, 300 DEG C were handled 0.5 hour, and it is 0.09 micron that average pore size is obtained after imidization, and the polyamides that porosity is 61.5% is sub-
Amine diaphragm.
Embodiment 3:Weigh (the NH that 11.25g average grain diameters are 0.03 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）It adds in above-mentioned solvent, treats diamines
After dissolving, by the pyromellitic dianhydride of 23.46g（PMDA）Substep is added in above-mentioned solvent, and 2 are stirred in the environment less than 30 DEG C
Hour, after vacuum outgas, obtain polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, is handled at 75 DEG C 4 hours, 90 DEG C of processing 20
Minute, 95 DEG C are handled 10 minutes, and 100 DEG C are handled 10 minutes, and 150 DEG C are handled 30 minutes, and 200 DEG C are handled 30 minutes, 250 DEG C of processing
30 minutes, 300 DEG C were handled 0.5 hour, and it is 0.05 micron that average pore size is obtained after imidization, and the polyamides that porosity is 37.8% is sub-
Amine diaphragm.
Embodiment 4:Weigh (the NH that 16.2g average grain diameters are 0.08 micron4)2C2O4It is scattered in 246gN, N- dimethyl second
It is spare in amide solution, the 4 of 25.85g is then weighed, 4 '-diaminodiphenyl ether（ODA）It adds in above-mentioned solvent, treats that diamines is molten
Xie Hou, by the pyromellitic dianhydride of 28.15g（PMDA）Substep is added in above-mentioned solvent, and it is small that 4 are stirred in the environment less than 30 DEG C
When, after vacuum outgas, obtain polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, is handled at 70 DEG C 3 hours, 90 DEG C handle 5 points
Clock, 95 DEG C are handled 10 minutes, and 100 DEG C are handled 10 minutes, and 150 DEG C are handled 30 minutes, and 200 DEG C are handled 30 minutes, 250 DEG C of processing 30
Minute, 300 DEG C are handled 0.5 hour, and it is 0.41 micron that average pore size is obtained after imidization, and porosity is 41.3% polyimides
Diaphragm.
Embodiment 5:Weigh (the NH that 6.75g average grain diameters are 0.15 micron4)2C2O4It is scattered in 246gN, N- dimethyl
It is spare in acetamide solution, the 4 of 20.99g is then weighed, 4 '-diaminodiphenyl ether（ODA）It adds in above-mentioned solvent, treats diamines
After dissolving, by the pyromellitic dianhydride of 24.01g（PMDA）Substep is added in above-mentioned solvent, is stirred in the environment less than 30 DEG C
2.5 hours, after vacuum outgas, obtain polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, is handled at 60 DEG C 5 hours, 90 DEG C of processing 10
Minute, 95 DEG C are handled 10 minutes, and 100 DEG C are handled 10 minutes, and 150 DEG C are handled 30 minutes, and 200 DEG C are handled 30 minutes, 250 DEG C of processing
30 minutes, 300 DEG C were handled 0.5 hour, and it is 0.41 micron that average pore size is obtained after imidization, and the polyamides that porosity is 41.3% is sub-
Amine diaphragm.
Embodiment 6:Weigh (the NH that 15.75g average grain diameters are 0.5 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）It adds in above-mentioned solvent, treats that diamines is molten
Xie Hou, by the pyromellitic dianhydride of 23.46g（PMDA）Substep is added in above-mentioned solvent, and it is small that 3 are stirred in the environment less than 30 DEG C
When, after vacuum outgas, obtain polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, is handled at 75 DEG C 4 hours, 90 DEG C of processing 20
Minute, 95 DEG C are handled 10 minutes, and 100 DEG C are handled 10 minutes, and 150 DEG C are handled 30 minutes, and 200 DEG C are handled 30 minutes, 250 DEG C of processing
30 minutes, 350 DEG C were handled 0.5 hour, and it is 0.59 micron that average pore size is obtained after imidization, and the polyamides that porosity is 51.6% is sub-
Amine diaphragm.
Embodiment 7:Weigh (the NH that 36g average grain diameters are 0.7 micron4)2C2O4It is scattered in 210gN, N- dimethylacetamides
It is spare in amine aqueous solution, the 4 of 42.46g is then weighed, 4 '-diaminodiphenyl ether（ODA）It adds in above-mentioned solvent, treats two amine solvents
Afterwards, by the pyromellitic dianhydride of 47.38g（PMDA）Substep is added in above-mentioned solvent, and it is small that 2.5 are stirred in the environment less than 30 DEG C
When, after vacuum outgas, obtain polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, is handled at 80 DEG C 2 hours, 90 DEG C of processing 30
Minute, 95 DEG C are handled 10 minutes, and 100 DEG C are handled 10 minutes, and 150 DEG C are handled 30 minutes, and 200 DEG C are handled 30 minutes, 250 DEG C of processing
30 minutes, 310 DEG C were handled 0.5 hour, and it is 0.87 micron that average pore size is obtained after imidization, and the polyamides that porosity is 49.3% is sub-
Amine diaphragm.
Embodiment 8:Weigh (the NH that 24g average grain diameters are 1 micron4)2C2O4It is scattered in 240gN, N- dimethylacetylamides
It is spare in solution, the 4 of 28.72g is then weighed, 4 '-diaminodiphenyl ether（ODA）It adds in above-mentioned solvent, after two amine solvents,
By the pyromellitic dianhydride of 31.28g（PMDA）Substep is added in above-mentioned solvent, stirs 4 hours in the environment less than 30 DEG C, very
After sky degassing, polyamic acid solution is obtained.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, is handled at 70 DEG C 1 hour, 80 DEG C of processing 2 are small
When, 90 DEG C are handled 20 minutes, and 95 DEG C are handled 10 minutes, and 100 DEG C are handled 10 minutes, and 150 DEG C are handled 30 minutes, 200 DEG C of processing 30
Minute, 250 DEG C are handled 30 minutes, and 350 DEG C are handled 0.5 hour, and it is 1.3 microns that average pore size is obtained after imidization, and porosity is
46.3% polyimide diaphragm.
Embodiment 9:Weigh (the NH that 9g average grain diameters are 0.03 micron4)2C2O4It is scattered in 240gN, N- dimethyl formyls
It is spare in amine aqueous solution, the 4 of 21.54g is then weighed, 4 '-diaminodiphenyl ether（ODA）It adds in above-mentioned solvent, treats two amine solvents
Afterwards, by the pyromellitic dianhydride of 23.46g（PMDA）Substep is added in above-mentioned solvent, and it is small that 2 are stirred in the environment less than 30 DEG C
When, after vacuum outgas, obtain polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, is handled at 65 DEG C 2.5 hours, 90 DEG C of processing
5 minutes, 95 DEG C were handled 5 minutes, and 100 DEG C are handled 10 minutes, and 150 DEG C are handled 30 minutes, and 200 DEG C are handled 30 minutes, 250 DEG C of processing
30 minutes, 350 DEG C were handled 0.5 hour, and it is 0.076 micron that average pore size is obtained after imidization, and the polyamides that porosity is 48.9% is sub-
Amine diaphragm.
Embodiment 10:Weigh (the NH that 9g average grain diameters are 0.03 micron4)2C2O4It is scattered in 240gN, N- dimethyl second
It is spare in amide solution, the 4 of 21.54g is then weighed, 4 '-diaminodiphenyl ether（ODA）It adds in above-mentioned solvent, treats that diamines is molten
Xie Hou, by the pyromellitic dianhydride of 23.46g（PMDA）Substep is added in above-mentioned solvent, and it is small that 2 are stirred in the environment less than 30 DEG C
When, after vacuum outgas, obtain polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, is handled at 65 DEG C 2.5 hours, 90 DEG C of processing
5 minutes, 95 DEG C were handled 5 minutes, and 100 DEG C are handled 10 minutes, and 150 DEG C are handled 30 minutes, and 200 DEG C are handled 30 minutes, 250 DEG C of processing
30 minutes, 350 DEG C were handled 0.5 hour, and it is 0.069 micron that average pore size is obtained after imidization, and the polyamides that porosity is 43.2% is sub-
Amine diaphragm.
Embodiment 11:Weigh (the NH that 9g average grain diameters are 0.06 micron4)2C2O4It is scattered in 240g methanol（Me）With four
Hydrogen furans（THF）In the mixed solvent（Wherein Me：THF=3:7, w:w）, the 4 of 21.54g is then weighed, 4 '-diaminodiphenyl ether
（ODA）It adds in above-mentioned solvent, after two amine solvents, by the pyromellitic dianhydride of 23.46g（PMDA）Substep adds in above-mentioned solvent
In, it is stirred 2 hours in the environment less than 30 DEG C, after vacuum outgas, obtains polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, is handled at 60 DEG C 2 hours, 90 DEG C handle 5 points
Clock, 95 DEG C are handled 5 minutes, and 100 DEG C are handled 10 minutes, and 150 DEG C are handled 30 minutes, and 200 DEG C are handled 30 minutes, 250 DEG C of processing 30
Minute, 350 DEG C are handled 0.5 hour, and it is 0.067 micron that average pore size is obtained after imidization, and porosity is 47.2% polyimides
Diaphragm.
Embodiment 12:Weigh (the NH that 1.8g average grain diameters are 0.06 micron4)2CO3It it is 0.8 micron with 7.2g average grain diameters
(NH4)2C2O4It is scattered in 240gN, it is spare in dinethylformamide solution, the 4 of 21.54g is then weighed, 4 '-diamino
Diphenyl ether（ODA）It adds in above-mentioned solvent, after two amine solvents, by the pyromellitic dianhydride of 23.46g（PMDA）On substep adds in
It states in solvent, is stirred 2 hours 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, baking oven is put into, is handled at 60 DEG C 5 hours, 90 DEG C of processing 5
Minute, 95 DEG C are handled 5 minutes, and 100 DEG C are handled 10 minutes, and 150 DEG C are handled 30 minutes, and 200 DEG C are handled 30 minutes, 250 DEG C of processing
30 minutes, 350 DEG C were handled 0.5 hour, and it is 0.83 micron that average pore size is obtained after imidization, and the polyamides that porosity is 48.9% is sub-
Amine diaphragm.
Embodiment 13:Weigh (the NH that 2.1g average grain diameters are 0.06 micron4)2CO3It it is 0.8 micron with 6.3g average grain diameters
(NH4)2C2O4It is scattered in 240gN, it is spare in dinethylformamide solution, the 4 of 21.54g is then weighed, 4 '-diamino
Diphenyl ether（ODA）It adds in above-mentioned solvent, after two amine solvents, by the pyromellitic dianhydride of 23.46g（PMDA）On substep adds in
It states in solvent, is stirred 2 hours 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, baking oven is put into, is handled at 60 DEG C 5 hours, 90 DEG C of processing 5
Minute, 95 DEG C are handled 5 minutes, and 100 DEG C are handled 10 minutes, and 150 DEG C are handled 30 minutes, and 200 DEG C are handled 30 minutes, 250 DEG C of processing
30 minutes, 350 DEG C were handled 0.5 hour, and it is 0.84 micron that average pore size is obtained after imidization, and the polyamides that porosity is 53.1% is sub-
Amine diaphragm.
Embodiment 14:Weigh (the NH that 4.5g average grain diameters are 0.06 micron4)2CO3It it is 0.8 micron with 4.5g average grain diameters
(NH4)2C2O4It is scattered in 240gN, it is spare in dinethylformamide solution, the 4 of 21.54g is then weighed, 4 '-diamino
Diphenyl ether（ODA）It adds in above-mentioned solvent, after two amine solvents, by the pyromellitic dianhydride of 23.46g（PMDA）On substep adds in
It states in solvent, is stirred 2 hours 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, baking oven is put into, is handled at 60 DEG C 5 hours, 90 DEG C of processing 5
Minute, 95 DEG C are handled 5 minutes, and 100 DEG C are handled 10 minutes, and 150 DEG C are handled 30 minutes, and 200 DEG C are handled 30 minutes, 250 DEG C of processing
30 minutes, 350 DEG C were handled 0.5 hour, and it is 0.83 micron that average pore size is obtained after imidization, and the polyamides that porosity is 59.3% is sub-
Amine diaphragm.
The composition do not mentioned in embodiment in composition disclosed in the invention described above can be in the above-described embodiments
The ingredient of alternative embodiment and form new embodiment.
If the pore former is ammonium oxalate, ammonium chloride, ammonium carbonate, ammonium hydrogen carbonate, ammonium nitrate, inferior ammonium nitrate, ammonium ceric nitrate
The combination of middle one or more, the pore former do not mentioned in above-mentioned composition can with alternate embodiment in the pore former mentioned
And form new embodiment.
The solvent is the solvent that can dissolve polyamic acid, specially n,N-dimethylacetamide（DMAc）, N, N- bis-
Methylformamide（DMF）, methanol and tetrahydrofuran one or more of mixed solvents, when with the mixed of methanol and tetrahydrofuran
When bonding solvent is solvent, on the basis of the gross mass of methanol and tetrahydrofuran, the content of tetrahydrofuran used is 70% ~ 80%, institute
It is 20% ~ 30% with the content of methanol；It is arbitrary ratio between each ingredient during other several combinations.It is not mentioned in above-mentioned composition
Solvent can be to be mentioned in alternate embodiment solvent.
The diamines is the monomer of common synthesis of polyimides, including 4,4 '-diaminodiphenyl ether, 3,4 '-diamino
Diphenyl ether, p-phenylenediamine, m-phenylene diamine (MPD), 5,4 '-diamino -2- phenyl benzoxazoles, 2-（4- aminophenyls）- 5 amino benzos
The arbitrary ratio of one or more of imidazoles, 4,4'- diamino -2,2'- dimethyl -1,1'- biphenyl, 4,4 '-benzidine
Combination.The diamines do not mentioned in above-mentioned composition can with alternate embodiment in the diamines mentioned and form new embodiment.
The dianhydride is the monomer of common synthesis of polyimides, including pyromellitic dianhydride, 3,3 ', 4, and 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 dianhydride do not mentioned in above-mentioned composition can with alternate embodiment in the dianhydride mentioned and formed
New embodiment.
Comparative example 1：The calcium carbonate that 18g 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 in 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, is stirred 3 hours 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 gradually polyimides to be obtained after imidization in an oven
Film.
Above-mentioned film with dilute hydrochloric acid solution is extracted repeatedly, calcium carbonate is removed, is then cleaned with distilled water to neutrality, and put
Baking oven drying is put, obtains 0.05 micron of aperture, the porous polyimide diaphragm of porosity 40%.
Claims (9)
1. a kind of preparation method of high porosity polyimide diaphragm, which is characterized in that the preparation method includes the following steps：
Step 1）, will heat and be capable of the inorganic salts pore former of decomposition gasification completely and be scattered in solvent at low temperature, be made and disperse
Liquid A；On the basis of the gross mass of solvent, the content of the pore former is 2.6% ~ 17.2%；
Step 2）, diamines is dissolved in above-mentioned dispersion liquid A, be then slowly added into dianhydride, stir 2 ~ 24 hours, obtain containing pore-forming
The polyamic acid solution of agent, wherein the molar ratio of the dianhydride and diamines is 0.98:1~1.05:1, with polyamic acid and solvent
On the basis of gross mass, the content of the polyamic acid is 15% ~ 30%, and the content of the solvent is 70% ~ 85%；
Step 3）, by above-mentioned polyamic acid solution plastic film mulch on a glass, being then placed in heating in baking oven makes solvent portion volatilize,
Gel or the film of self-supporting state are obtained, continuing heating is thermally decomposed pore former, makes film pore-forming, and continuing heating makes film imidization
Porous polyimide diaphragm is obtained afterwards.
2. a kind of preparation method of high porosity polyimide diaphragm according to claim 1, which is characterized in that in step 1）
Described in pore former be ammonium oxalate, ammonium chloride, ammonium carbonate, ammonium hydrogen carbonate, ammonium nitrate, inferior ammonium nitrate, it is a kind of in ammonium ceric nitrate or
Several combinations, the average grain diameter of the pore former is 0.03 ~ 1 micron.
3. a kind of preparation method of high porosity polyimide diaphragm according to claim 1, which is characterized in that in step 1）
Described in low temperature dispersion temperature be -5 ~ 30 DEG C.
A kind of 4. preparation method of high porosity polyimide diaphragm according to claim 1, which is characterized in that the solvent
For the solvent of polyamic acid, specially n,N-dimethylacetamide can be dissolved（DMAc）, N,N-dimethylformamide（DMF）、
Any one of mixed solvent of methanol and tetrahydrofuran, when using the mixed solvent of methanol and tetrahydrofuran as solvent, with first
On the basis of the gross mass of alcohol and tetrahydrofuran, the content of tetrahydrofuran used is 70% ~ 80%, the content of methanol used for 20% ~
30%。
A kind of 5. preparation method of high porosity polyimide diaphragm according to claim 1, which is characterized in that the pore-forming
The decomposition gasification temperature of agent is no more than 400 DEG C.
A kind of 6. preparation method of high porosity polyimide diaphragm according to claim 1, which is characterized in that the diamines
For the monomer of common synthesis of polyimides, including 4,4 '-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, p-phenylenediamine,
M-phenylene diamine (MPD), 5,4 '-diamino -2- phenyl benzoxazoles, 2-（4- aminophenyls）- 5 aminobenzimidazoles, 4,4'- diamino-
Any combination of one or more of 2,2'- dimethyl -1,1'- biphenyl, 4,4 '-benzidine.
A kind of 7. preparation method of high porosity polyimide diaphragm according to claim 1, which is characterized in that the dianhydride
For the monomer of common synthesis of polyimides, including pyromellitic dianhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 2,2 ',
The arbitrary of one or more of 3,3 '-bibenzene tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride (BTDA), Bisphenol A Type Diether Dianhydride compares group
It closes.
8. a kind of preparation method of high porosity polyimide diaphragm according to claim 1, which is characterized in that it is described make it is molten
Agent part volatilization processing procedure be to be handled 1 ~ 5 hour at 60 ~ 90 DEG C, it is described thermally decomposed pore former processing procedure be
It is handled 5 ~ 30 minutes at 90 ~ 100 DEG C, the processing procedure of the imidization is handled 0.5 ~ 1 hour at 150 ~ 300 DEG C.
9. a kind of high porosity polyimide diaphragm, which is characterized in that the high porosity polyimide diaphragm is using right
It is required that prepared by the preparation method of 1 ~ 8 any high porosity polyimide diaphragm.
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Cited By (6)
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| CN110112352A (en) * | 2019-06-17 | 2019-08-09 | 合肥国轩高科动力能源有限公司 | Polyimide diaphragm and preparation method and application thereof |
| 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 |
| CN113121857A (en) * | 2021-06-01 | 2021-07-16 | 桂林电器科学研究院有限公司 | Low-dielectric-property polyimide film and preparation method thereof |
| CN115832607A (en) * | 2021-09-18 | 2023-03-21 | 宁德时代新能源科技股份有限公司 | Preparation method of battery diaphragm, battery diaphragm and secondary battery |
| WO2023074909A1 (en) * | 2021-11-01 | 2023-05-04 | 株式会社スリーダムアライアンス | Polyimide porous film, electrode structure, and power storage device |
| 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 |
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| CN102916149A (en) * | 2012-09-26 | 2013-02-06 | 东莞市创明电池技术有限公司 | Micropore membrane of lithium battery and preparation technique for micropore membrane |
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| CN110112352A (en) * | 2019-06-17 | 2019-08-09 | 合肥国轩高科动力能源有限公司 | Polyimide diaphragm and preparation method and application thereof |
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| WO2023074909A1 (en) * | 2021-11-01 | 2023-05-04 | 株式会社スリーダムアライアンス | Polyimide porous film, electrode structure, and power storage device |
| 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 |
| CN116315447B (en) * | 2023-05-04 | 2023-08-01 | 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 |
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Application publication date: 20180615 |