CN102816431B - Superfine fiber porous film and preparation method and application thereof - Google Patents
Superfine fiber porous film and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a superfine fiber porous film which is prepared by subjecting polyamide-amido acid former polymer solution obtained by polymerization of 4, 4'-diamidobenzanilide and one or multiple of aromatic tetracid dihydride. The structure of the 4, 4'-diamidobenzanilide is shown as a formula (1). The superfine fiber porous film has the advantages of good wettability with electrolyte, high porosity, high-temperature resistance, high strength, high chemical stability and the like, and is quite suitable for being used as a battery diaphragm. The invention further provides a preparation method of the superfine fiber porous film and the application of the same as the battery diaphragm.
Description
Technical field
The present invention relates to a kind of superfine fiber porous membrane, be specifically related to a kind of high porosity, high strength, resistant to elevated temperatures superfine fiber porous membrane, and preparation method thereof and as the application of battery diaphragm.
Background technology
Battery diaphragm is the important component part in battery product, and its effect is to allow ion to pass through when preventing two electrode physical contacts.The resistance of barrier film is directly proportional to its thickness, is inversely proportional to porosity.In order to reduce the internal resistance of battery product, to the requirement of barrier film be: a) ultra-thin; B) high porosity; C) high strength.Normally used material has glass fibre, polyethylene porous membrane and polypropylene porous film etc.Just actively research and develop in the market novel diaphragm material.Du pont company adopts melting pneumoelectric spray spinning technique to prepare Energain polyimide nano-fiber battery diaphragm, starts volume production kind electrode separating diaphragm in U.S. Wilmington and South Korea Seoul at present, and this class barrier film can improve battery power prolongs life.Jiangxi Xian Cai nanofiber Science and Technology Ltd. adopts solution electrostatic spinning process to prepare the polyimide battery barrier film of self-supporting first, and patent applied for.Just actively polyimide diaphragm is introduced to the market at present, build the back yard industry production line of the polyimide nano-fiber non-woven of 2000 square metres of daily outputs, make first of world solution electrostatic spinning suitability for industrialized production demonstration line, the production line of 200,000,000 square metres of polyimide nano-fiber non-wovens of annual output under preparation.
The present invention, under above-mentioned background, through continuing further investigation, proposes a kind of new battery diaphragm, has high porosity, high strength, the high feature such as anti-acupuncture intensity and high thermal stability simultaneously.
Summary of the invention
One object of the present invention is to provide a kind of superfine fiber porous membrane, has high porosity, high strength, resistant to elevated temperatures feature, meets the high request of battery diaphragm.
Another object of the present invention is: the preparation method that described superfine fiber porous membrane is provided.
A further object of the present invention is: the application of described superfine fiber porous membrane as battery diaphragm is provided.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of superfine fiber porous membrane is provided, and it is that before the polymeric amide-amido acid being obtained by 4,4'-diaminobenzene anilide and one or more aromatic series tetracarboxylic dianhydride polymerizations, aggressiveness solution prepares through electrostatic spinning and imidization processing; Described 4,4'-diaminobenzene anilide structure as the formula (1)
In the preferred superfine fiber porous membrane of the present invention, one or more described aromatic series tetracarboxylic dianhydrides are selected from one or more the mixture in BPDA, xenol diether tetracarboxylic dianhydride, triphen diether tetracarboxylic dianhydride, sulfobenzide tetracarboxylic dianhydride, hexafluoro tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, dicyclo octene tetracarboxylic dianhydride, diphenyl sulfide tetracarboxylic dianhydride, phenyl ether tetracarboxylic dianhydride, dimethyl diphenyl silane tetracarboxylic dianhydride, dihydroxyphenyl propane tetracarboxylic dianhydride or pyromellitic acid dianhydride; The mixture of one or more in further preferred bibenzene tetracarboxylic dianhydride, pyromellitic acid dianhydride, benzophenone dianhydride, diphenyl sulfone dianhydride or triphen two ether dianhydrides.
A kind of preferred superfine fiber porous membrane of the present invention is that before the polymeric amide-amido acid being obtained by 4,4'-diaminobenzene anilide and the polymerization of a kind of aromatic series tetracarboxylic dianhydride, aggressiveness solution prepares through electrostatic spinning and imidization processing; Described ultra-fine fibre has the structure shown in formula (2):
Wherein, R is the residue structure containing the dianhydride of aromatic ring; N is polymer repeat unit number, between 100 to 1000.N value is larger, and polymericular weight is larger, to form ultra-fine fibre intensity higher.
In the further preferred superfine fiber porous membrane of the present invention, described R is selected from the one in following concrete structure:
In superfine fiber porous membrane of the present invention, described preferably 50 ~ 1500nm of ultra-fine fibre diameter.
The preparation method of the superfine fiber porous membrane described in the present invention also provides, comprises the following steps:
(1) configuration of electrostatic spinning solution: by 4,4'-diaminobenzene anilide and aromatic series tetracarboxylic dianhydride according to the mixed in molar ratio of 0.9-1.1:1.1-0.9 after, be dissolved in 6-10 doubly in the solvent of reaction mixture gross weight, polyreaction 2-8 hour at-10 ℃～15 ℃, obtain polymeric amide-amido acid solution, the limiting viscosity of polymkeric substance is 1.0-4.5dl/g, and the mass percentage concentration of adjusting solution is 8%-25%, as electrostatic spinning solution for standby;
(2) preparation of electric-woven super-fine fiber non-woven: carry out electrospinning in the high-voltage electric field that is 100-400kV/m with solution in strength of electric field by the electrostatic spinning of step (1) modulation, form polymeric amide-amido acid ultra-fine fibre, adopt stainless steel guipure to collect polymeric amide-amido acid not weaving fabric of superfine fiber;
(3) imidization: the polymeric amide-amido acid not weaving fabric of superfine fiber obtaining in step (2) is rapidly heated to 250 ℃ from room temperature with the heat-up rate of 20 ℃/min, and constant temperature stops 20min; Continue to be warming up to 350 ℃ with the temperature rise rate of 10 ℃/min again, and be cooled to room temperature after stopping 20min, obtain the polyamide-imide superfine fiber porous membrane of rock steady structure.
The solvent that the described polyreaction of step (1) is used is preferably N, the mixed solvent of one or more in dinethylformamide (DMF), N-Methyl pyrrolidone (NMP), N,N-dimethylacetamide (DMAC) or dimethyl sulfoxide (DMSO) (DMSO).
The described adjustment polymers soln mass percent concentration of step (1) preferably by adding ethanol or tetrahydrofuran (THF) completes in solution.
The described stainless steel guipure preferable width of step (2) is 1 meter, and tape running speed is 0.5-10.0m/min.
In above-mentioned preparation method, 4,4'-diaminobenzene anilide and a kind of aromatic series tetracarboxylic dianhydride synthesizing polyamides acid-acid amides, then under the condition of high temperature, be converted into the transition process of polyamide-imide, as follows, wherein, the definition of R, n is the same.
In addition 4,4'-diaminobenzene anilide becomes polyamic acid-acid amides with two or more aromatic series tetracarboxylic dianhydrides, then it is similar under the condition of high temperature, to be converted into transition process and the said process of polyamide-imide.
Superfine fiber porous membrane described in the present invention also provides is as the application of battery diaphragm.
Polyamide-imide superfine fiber porous membrane of the present invention is by forming the polyamide-imide superfine fibre porous membrane material with rock steady structure after the imidization of polymeric amide-acyl acid amide high temperature, compared with prior art, the beneficial effect major embodiment of porous-film of the present invention has the excellent properties of the following aspects at the same time:
1. its chemical composition is mainly made up of the good aromatic compound of thermotolerance, thereby has high heat resistance.
2. the pore texture of porous-film of the present invention is built by the random accumulation of ultra-fine fibre, causes and makes it have high porosity.
3. due to 4, in this diamine monomer of 4'-diaminobenzene anilide, contain amide group (CONH-), in the polymer architecture obtaining through imidization after itself and dianhydride monomer condensation polymerization, both contained imide group, also remain with original amide group (CONH-) in diamine monomer, thereby making has in a large number and can exist with the reactive hydrogen of the intermolecular formation hydrogen bond of electrolytic solution on fiber surface or hole wall surface, make this porous-film in the time using as battery diaphragm, and between electrolytic solution, there is good wetting property.
4. in ultra-fine fibre of the present invention, intermolecular a large amount of hydrogen bonds make to have formed two-dimensional network structure between parallel macromolecular chain, this is conducive to improve tensile strength, shearing resistance, shearing modulus and the compressive strength of fiber, thereby the mechanical property while significantly improving superfine fiber porous membrane of the present invention as battery diaphragm, as improve tensile strength and the acupuncture intensity etc. of battery diaphragm product.
The performance of this polyamide-imide superfine fibre porous membrane material that in a word, prepared by the present invention can be summarized as follows: its Fibre diameter is at 50 ~ 1500nm; Tensile strength can reach 30 ~ 100MPa, and most cases is greater than 50MPa; Porosity can reach 70% ~ 90%; Acupuncture intensity is greater than 3.0N; Under 250 ℃ of conditions, vertical and horizontal zero shrink; In organic solvent, there is not chemical reaction completely; In electrolytic solution, wetting property is good.
Embodiment
Following examples will contribute to those of ordinary skill in the art further to understand the present invention, but not limit in any form the present invention.
Embodiment 1
Bibenzene tetracarboxylic dianhydride/4, the preparation of 4'-diaminobenzene anilide (BPDA/DABA) polyamide-imide ultra-fine fibre battery diaphragm
1) DABA is added to solvent N, in dinethylformamide (DMF), be stirred to completely and dissolve, mol ratio according to 1:1 adds BPDA, polycondensation 5 hours at 5 ℃, obtaining mass concentration is 10%, and polymer property viscosity is 2.6dl/g, aggressiveness (polymeric amide-amido acid) solution before the polyamide-imide that solution absolute viscosity is 5.1PaS.
2) in the electric field that polymeric amide-amido acid solution step 1) being obtained is 250kV/m in strength of electric field, implement electrostatic spinning, collect polymeric amide-amido acid not weaving fabric of superfine fiber take stainless (steel) wire as collector.
3) by step 2) polymeric amide-amido acid not weaving fabric of superfine fiber of obtaining is placed in High Temperature Furnaces Heating Apparatus, imidization under nitrogen atmosphere.Heating schedule is: the temperature rise rate with 20 ℃/min is rapidly heated to 250 ℃ from room temperature, and stops 20min at this temperature; Continue to be warming up to 350 ℃ with the temperature rise rate of 10 ℃/min, drop to room temperature stop 20min at this temperature after, obtain polyamide-imide ultra-fine fibre battery diaphragm.
The tensile strength of test gained battery diaphragm is 50MPa, and elongation at break is 10%, and porosity is 82%, and acupuncture intensity is 3.8N; Vertical, horizontal shrinking percentage at 250 ℃ is 0.
Embodiment 2
BPDA/pyromellitic acid dianhydride/4, the preparation of 4'-diaminobenzene anilide (BPDA/PMDA/DABA) polyamide-imide ultra-fine fibre battery diaphragm
1) BPDA:PMDA:DABA is joined to N according to the mol ratio of 0.5:0.5:1.0, in N-N,N-DIMETHYLACETAMIDE (DMAC), polycondensation 6 hours at 0 ℃, obtaining mass concentration is 10%, polymer property viscosity is 1.9dl/g, aggressiveness (polymeric amide-amido acid) solution before the polyamide-imide that solution absolute viscosity is 4.5PaS.
2) in the electric field that polymeric amide-amido acid solution step 1) being obtained is 300kV/m in strength of electric field, implement electrostatic spinning, collect polymeric amide-amido acid not weaving fabric of superfine fiber take stainless (steel) wire as collector.
3) by step 2) polymeric amide-amido acid not weaving fabric of superfine fiber of obtaining is placed in High Temperature Furnaces Heating Apparatus, imidization under nitrogen atmosphere.Heating schedule is: the temperature rise rate with 20 ℃/min is rapidly heated to 250 ℃ from room temperature, and stops 20min at this temperature; Continue to be warming up to 380 ℃ with the temperature rise rate of 10 ℃/min, drop to room temperature stop 20min at this temperature after, obtain polyamide-imide ultra-fine fibre battery diaphragm.
The tensile strength of test gained battery diaphragm is 40MPa, and elongation at break is 8%, and porosity is 85%, and acupuncture intensity is 3.0N; Vertical, horizontal shrinking percentage at 250 ℃ is 0.
Embodiment 3
Benzophenone dianhydride/diphenyl sulfone dianhydride/4, the preparation of 4'-diaminobenzene anilide (BTDA/DSDA/DABA) polyimide-acid amides nanofiber battery diaphragm
1) BTDA, DSDA and DABA are joined to N according to the mol ratio of 0.5:0.5:1.0, in N-N,N-DIMETHYLACETAMIDE (DMAC), condensation polymerization 5 hours at-5 ℃, obtaining mass concentration is 12%, polymer property viscosity is 2.1dl/g, aggressiveness (polymeric amide-amido acid) solution before the polyamide-imide that solution absolute viscosity is 4.7PaS.
2) in the electric field that polymeric amide-amido acid solution step 1) being obtained is 200kV/m in strength of electric field, implement electrostatic spinning, collect polymeric amide-amido acid not weaving fabric of superfine fiber take stainless (steel) wire as collector.
3) by step 2) polymeric amide-amido acid not weaving fabric of superfine fiber of obtaining is placed in High Temperature Furnaces Heating Apparatus, imidization under nitrogen atmosphere.Heating schedule is: the temperature rise rate with 20 ℃/min is rapidly heated to 250 ℃ from room temperature, and stops 20min at this temperature; Continue to be warming up to 350 ℃ with the temperature rise rate of 10 ℃/min, drop to room temperature stop 20min at this temperature after, obtain polyamide-imide ultra-fine fibre battery diaphragm.
The tensile strength of test gained battery diaphragm is 35MPa, and elongation at break is 11%, and porosity is 86%, and acupuncture intensity is 2.5N; Vertical, horizontal shrinking percentage at 250 ℃ is 0.
Embodiment 4
Pyromellitic acid dianhydride/triphen two ether dianhydride/4, the preparation of 4'-diaminobenzene anilide (PMDA/RsPDA/DABA) polyimide-acid amides nanofiber battery diaphragm
1) by PMDA, RsPDA and DABA according to 0.5:0.5:1.0 mixed in molar ratio, N-Methyl pyrrolidone (NMP) and N take volume ratio as 1:1, the mixing solutions of N-methylacetamide (DMAC) is as solvent, condensation polymerization 8 hours at 10 ℃, obtaining mass concentration is 15%, polymer property viscosity is 2.0dl/g, aggressiveness (polymeric amide-amido acid) solution before the polyamide-imide that solution absolute viscosity is 5.5PaS.
2) in the electric field that polymeric amide-amido acid solution step 1) being obtained is 300kV/m in strength of electric field, implement electrostatic spinning, collect polymeric amide-amido acid not weaving fabric of superfine fiber take stainless (steel) wire as collector.
3) by step 2) polymeric amide-amido acid not weaving fabric of superfine fiber of obtaining is placed in High Temperature Furnaces Heating Apparatus, imidization under nitrogen atmosphere.Heating schedule is: the temperature rise rate with 20 ℃/min is rapidly heated to 250 ℃ from room temperature, and stops 20min at this temperature; Continue to be warming up to 330 ℃ with the temperature rise rate of 10 ℃/min, drop to room temperature stop 20min at this temperature after, obtain polyamide-imide ultra-fine fibre battery diaphragm.
The tensile strength of test gained battery diaphragm is 70MPa, and elongation at break is 12%, and porosity is 81%, and acupuncture intensity is 5.5N; Vertical, horizontal shrinking percentage at 250 ℃ is 0.
Embodiment 5
Biphenyl dianhydride/diphenyl sulfone dianhydride/4, the preparation of 4'-diaminobenzene anilide (BPDA/DSDA/DABA) polyimide-acid amides nanofiber battery diaphragm
1) by PMDA, DSDA and DABA according to 0.5:0.5:1.0 mixed in molar ratio, N-Methyl pyrrolidone (NMP) and N take volume ratio as 1:1, the mixing solutions of N-N,N-DIMETHYLACETAMIDE (DMAC) is as solvent, condensation polymerization 5 hours at 5 ℃, obtaining mass concentration is 11%, polymer property viscosity is 2.4dl/g, aggressiveness (polymeric amide-amido acid) solution before the polyamide-imide that solution absolute viscosity is 4.8PaS.
2) in the electric field that polymeric amide-amido acid solution step 1) being obtained is 250kV/m in strength of electric field, implement electrostatic spinning, collect polymeric amide-amido acid not weaving fabric of superfine fiber take stainless (steel) wire as collector.
3) by step 2) polymeric amide-amido acid not weaving fabric of superfine fiber of obtaining is placed in High Temperature Furnaces Heating Apparatus, imidization under nitrogen atmosphere.Heating schedule is: the temperature rise rate with 20 ℃/min is rapidly heated to 250 ℃ from room temperature, and stops 20min at this temperature; Continue to be warming up to 380 ℃ with the temperature rise rate of 10 ℃/min, drop to room temperature stop 20min at this temperature after, obtain polyamide-imide ultra-fine fibre battery diaphragm.
The tensile strength of test gained battery diaphragm is 55MPa, and elongation at break is 10%, and porosity is 83%, and acupuncture intensity is 4.0N; Vertical, horizontal shrinking percentage at 250 ℃ is 0.
Above-described embodiment is only the preferred embodiments of the present invention, can not limit protection scope of the present invention with this, and the variation of any unsubstantiality that those skilled in the art does on basis of the present invention and replacement all belong to the present invention's scope required for protection.
Claims (8)
1. a superfine fiber porous membrane, is characterized in that: it is that before the polymeric amide-amido acid being obtained by 4,4'-diaminobenzene anilide and two or more aromatic series tetracarboxylic dianhydride polymerization, aggressiveness solution prepares through electrostatic spinning and imidization processing; Described 4,4'-diaminobenzene anilide structure as the formula (1)
Described superfine fiber porous membrane is prepared by following methods:
(1) configuration of electrostatic spinning solution: by 4,4'-diaminobenzene anilide and aromatic series tetracarboxylic dianhydride according to the mixed in molar ratio of 0.9-1.1:1.1-0.9 after, be dissolved in 6-10 doubly in the solvent of reaction mixture gross weight, polyreaction 2-8 hour at-10 ℃～15 ℃, obtain polymeric amide-amido acid solution, the limiting viscosity of polymkeric substance is 1.0-4.5dl/g, and the mass percentage concentration of adjusting solution is 8%-25%, as electrostatic spinning solution for standby;
(2) preparation of electric-woven super-fine fiber non-woven: carry out electrospinning in the high-voltage electric field that is 100-400kV/m with solution in strength of electric field by the electrostatic spinning of step (1) modulation, form polymeric amide-amido acid ultra-fine fibre, adopt stainless steel guipure to collect polymeric amide-amido acid not weaving fabric of superfine fiber;
(3) imidization: the polymeric amide-amido acid not weaving fabric of superfine fiber obtaining in step (2) is rapidly heated to 250 ℃ from room temperature with the heat-up rate of 20 ℃/min, and constant temperature stops 20min; Continue to be warming up to 350 ℃ with the temperature rise rate of 10 ℃/min again, and be cooled to room temperature after stopping 20min, obtain the polyamide-imide superfine fiber porous membrane of rock steady structure.
2. superfine fiber porous membrane claimed in claim 1, is characterized in that: described two or more aromatic series tetracarboxylic dianhydride is selected from the two or more mixture in BPDA, xenol diether tetracarboxylic dianhydride, triphen diether tetracarboxylic dianhydride, sulfobenzide tetracarboxylic dianhydride, hexafluoro tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, diphenyl sulfide tetracarboxylic dianhydride, phenyl ether tetracarboxylic dianhydride, dimethyl diphenyl silane tetracarboxylic dianhydride, dihydroxyphenyl propane tetracarboxylic dianhydride or pyromellitic acid dianhydride.
3. superfine fiber porous membrane claimed in claim 2, is characterized in that: described two or more aromatic series tetracarboxylic dianhydride is selected from the two or more mixture in bibenzene tetracarboxylic dianhydride, pyromellitic acid dianhydride, benzophenone dianhydride, diphenyl sulfone dianhydride or triphen two ether dianhydrides.
4. superfine fiber porous membrane claimed in claim 1, is characterized in that: described ultra-fine fibre diameter is at 50～1500nm.
5. the preparation method of superfine fiber porous membrane claimed in claim 1, comprises the following steps:
(1) configuration of electrostatic spinning solution: by 4,4'-diaminobenzene anilide and aromatic series tetracarboxylic dianhydride according to the mixed in molar ratio of 0.9-1.1:1.1-0.9 after, be dissolved in 6-10 doubly in the solvent of reaction mixture gross weight, polyreaction 2-8 hour at-10 ℃～15 ℃, obtain polymeric amide-amido acid solution, the limiting viscosity of polymkeric substance is 1.0-4.5dl/g, and the mass percentage concentration of adjusting solution is 8%-25%, as electrostatic spinning solution for standby;
(2) preparation of electric-woven super-fine fiber non-woven: carry out electrospinning in the high-voltage electric field that is 100-400kV/m with solution in strength of electric field by the electrostatic spinning of step (1) modulation, form polymeric amide-amido acid ultra-fine fibre, adopt stainless steel guipure to collect polymeric amide-amido acid not weaving fabric of superfine fiber;
(3) imidization: the polymeric amide-amido acid not weaving fabric of superfine fiber obtaining in step (2) is rapidly heated to 250 ℃ from room temperature with the heat-up rate of 20 ℃/min, and constant temperature stops 20min; Continue to be warming up to 350 ℃ with the temperature rise rate of 10 ℃/min again, and be cooled to room temperature after stopping 20min, obtain the polyamide-imide superfine fiber porous membrane of rock steady structure.
6. preparation method claimed in claim 5, is characterized in that: the described aromatic series tetracarboxylic dianhydride of step (1) is selected from the two or more mixture in BPDA, xenol diether tetracarboxylic dianhydride, triphen diether tetracarboxylic dianhydride, sulfobenzide tetracarboxylic dianhydride, hexafluoro tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, diphenyl sulfide tetracarboxylic dianhydride, phenyl ether tetracarboxylic dianhydride, dimethyl diphenyl silane tetracarboxylic dianhydride, dihydroxyphenyl propane tetracarboxylic dianhydride or pyromellitic acid dianhydride.
7. preparation method claimed in claim 5, is characterized in that: the described solvent of step (1) is one or more the mixed solvent in DMF, N-Methyl pyrrolidone, N,N-dimethylacetamide or dimethyl sulfoxide (DMSO); The described stainless (steel) wire bandwidth of step (2) is 1 meter, and tape running speed is 0.5-10.0m/min.
8. superfine fiber porous membrane claimed in claim 1 is as the application of battery diaphragm.
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| CN102251307A (en) * | 2011-05-30 | 2011-11-23 | 中国科学院青岛生物能源与过程研究所 | Polyimide-base nano fibrous membrane, and preparation method and application thereof |
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| "含有氢键的聚酰亚胺薄膜的制备和性能表征";申晓华 等;《高分子材料科学与工程》;20120531;第28卷(第5期);第125-128页，正文第1.1-2.3节 * |
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| EP4079790A1 (en) * | 2021-04-19 | 2022-10-26 | Nitto Denko Corporation | Porous polyimide film |
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