CN101280085B - Preparation of porous film material - Google Patents
Preparation of porous film material Download PDFInfo
- Publication number
- CN101280085B CN101280085B CN2008100282500A CN200810028250A CN101280085B CN 101280085 B CN101280085 B CN 101280085B CN 2008100282500 A CN2008100282500 A CN 2008100282500A CN 200810028250 A CN200810028250 A CN 200810028250A CN 101280085 B CN101280085 B CN 101280085B
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- Prior art keywords
- thin
- sheet
- phase resin
- preparation
- film
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000463 material Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000010409 thin film Substances 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 49
- 239000010408 film Substances 0.000 claims description 42
- 238000001816 cooling Methods 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 abstract description 18
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 238000005191 phase separation Methods 0.000 abstract 1
- 239000004743 Polypropylene Substances 0.000 description 12
- 229920001903 high density polyethylene Polymers 0.000 description 12
- 239000004700 high-density polyethylene Substances 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- -1 polypropylene Polymers 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 229920000092 linear low density polyethylene Polymers 0.000 description 4
- 239000004707 linear low-density polyethylene Substances 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- 239000004702 low-density polyethylene Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 108090000862 Ion Channels Proteins 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000000739 chaotic effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a preparation method for porous membrane materials; continuous phase resin materials, separation phase resin materials and other additives are evenly mixed to prepare lending material; the blending material is made into thin film sheets which are then processed with tension phase separation, so that the joints between the molecules of the continuous phase resin materials and the molecules of the separation phase resin materials in the sheets are broken to form clearance holes, so as to get the material. The method of the invention has the advantages of simple technology, less processing procedures, low production costs and high efficiency. The molecules of different phase resin materials in the sheets are evenly distributed; through physical tension sheets, the intermolecular joints of different phase materials in the sheets are broken and form clearance holes which are evenly distributed and have good hole-shaped structures as well as good mechanical properties.
Description
Technical field
The present invention relates to a kind of preparation method, the preparation method of the porous film material that particularly a kind of lithium ion battery is used with film of vesicular structure.
Background technology
The barrier film of polymer lithium ion battery is a kind of high molecular film material with vesicular structure; its lithium ion that can be in the battery provides ionic channel; can improve the cycle charge-discharge time of lithium ion battery; improve the specific storage of lithium ion battery to a certain extent, and can play the effect of protection lithium ion battery safe handling.
At present, the manufacture method of high-polymer lithium battery porous diaphragm mainly contains two kinds of dry method and wet methods.Dry method is added nucleator in thin-film sheet, after the β nucleation, thin-film sheet through two-way or unilateral stretching, is caused the subsiding pore-forming of β nucleus and makes.The thin-film material that it makes, mechanical property is relatively poor, the hole shape structure is bad, multidigit is elongated and structure is comparatively chaotic, and producing apparatus and technology are also comparatively complicated simultaneously.
Wet method forms homogeneous system by the equal resin of polymkeric substance is mixed with partial solvent, and general's solvent extraction wherein falls pore-forming and makes again.This method processing process is long, complex procedures, and the product aperture is big, the hole shape structure is confusing.In addition, need to adopt a large amount of volatile solvents, contaminate environment in the production process.
Summary of the invention
The object of the present invention is to provide a kind of good mechanical performance, pore distribution evenly, hole shape well-formed, production technique be simple, and than the preparation method of the porous film material of environmental protection.
A kind of porous diaphragm preparation methods comprises the step of telling order down:
1. with external phase resin material 50%～90%, separate phase resin material 10%～50%, and other 0%～2.5% even mixing of auxiliary agent, blend composition made;
2. the blend composition of gained is made thin-film sheet;
3. the processing that is separated stretches the thin-film sheet that makes, promptly thin-film sheet is carried out unidirectional or two-way drawing high, the molecule that makes the external phase resin material in the sheet material with separate mutually the intermolecular junction of resin material and rupture, produce the gap, thereby make porous film material.
The preparation method of porous film material of the present invention, technology is simple, manufacturing procedure is few, production cost is low, efficient is high.It is by the physics stretched sheet, make the intermolecular generation fracture generation mesopore of different phase materials in the sheet material, sheet material by the external phase resin material with separate phase resin material uniform mixing after make, not homophase resin material molecular distribution in the sheet material is more even, thereby the mesopore that the back fracture that stretches produces is evenly distributed, hole shape well-formed, mechanical property are good.Simultaneously, do not need to use volatile solvent in the production process of thin-film material, thereby also environmental protection more.
Embodiment
Embodiment 1, and a kind of preparation method of porous film material comprises the step of following order:
1. external phase resin material HDPE (high density polyethylene(HDPE)) is pressed 60% weight percent, separation phase resin material PP (polypropylene) presses 40% the white proportion by subtraction of weight, and other auxiliary agent antioxidant 1010 is made blend composition by 1% weight percent uniform mixing;
2. the blend composition of gained is made thin-film sheet;
3. the processing that is separated stretches the thin-film sheet that makes, promptly thin-film sheet is carried out unidirectional or two-way drawing high, the molecule that makes the external phase resin material in the sheet material with separate mutually the intermolecular junction of resin material and rupture, produce the gap, thereby prepare the porous diaphragm material.
Wherein, 1. step prepares blend composition can use Banbury mixer, mill, also can use the twin screw extruder moulding.In above-mentioned forming method, with external phase resin material HDPE (high density polyethylene(HDPE)) with separate resin material PP (polypropylene) mutually, and oxidation inhibitor joins that the blend granulation prepares blend composition in the molding device.
For making the blend composition that obtains more even, adopt the twin screw extruder moulding preferable, particularly adopt the twin screw extruder of length-to-diameter ratio 〉=25 (being generally 25～45) to handle good especially.
2. step prepares thin-film sheet can use the blown film method, also can use the hydrostomia method, especially can use the two-way stretch method.
When using the blown film method, the 1. prepared blend composition of step is added in the forcing machine, blend composition after forcing machine melt extrudes, through port mould shape film forming pipe; The film pipe blasts pressurized air through vane, makes film pipe inflation, makes it cooling and shaping by formed frame again, then flattens the film pipe with collapser, promptly makes the film sheet of institute's required thickness and wide cut.
When using the hydrostomia method, the blend composition that 1. step is made joins in the forcing machine, and melt through the cooling of chilling roller, promptly is shaped to needed thin-film sheet again through die head hydrostomia casting sheet behind the forcing machine plastifying fusion.
When using the two-way stretch method, the blend composition that 1. step is made joins in the forcing machine, and longitudinal stretching or cross directional stretch are carried out in preheating behind hydrostomia cooling casting sheet then respectively, after heat treatment cut edge, and promptly make needed thin-film sheet; Or the 1. prepared masterbatch of step joined in the forcing machine, behind plastifying fusion, being extruded into pipe by the molding port mould, longitudinal stretching behind inflation is cut edge through thermal treatment again, promptly makes needed thin-film sheet.
The thin-film sheet that 2. step of the present invention is made can be thickness 100～1000um, the thin-film sheet of width 300mm～5m; The preferably thin-film sheet of thickness 500～800um; This thickness deviation preferably is controlled in 5%.
3. step stretches the thin-film sheet that makes on drawing machine, the molecule that makes the external phase resin material in the sheet material with separate mutually the intermolecular junction of resin material and rupture, produce mesopore.Sheet material can only carry out longitudinal stretching on longitudinal stretching machine, also can only on the cross directional stretch machine, carry out cross directional stretch, also but two-way stretch (promptly both stretched on longitudinal stretching machine, on the cross directional stretch machine, stretch again), as first longitudinal stretching cross directional stretch again, or first cross directional stretch longitudinal stretching again, wherein, being good through two-way stretch.
Embodiment 2, and 2. a kind of preparation method of porous film material, its step make the thick 300um of being of diaphragm material, and film is wide to be 0.2m.Its step 3. in thin-film sheet through two-way stretch, its first longitudinal stretching, draft temperature are 90 ℃, draw ratio is 2.0 times, again through cross directional stretch, draft temperature is 100 ℃, draw ratio is 5 times.All the other are identical with embodiment 1.
Embodiment 3, and 2. a kind of preparation method of porous film material, its step make the thick 375um of being of diaphragm material, and film is wide to be 0.6m.Its step 3. in thin-film sheet through two-way stretch, its first longitudinal stretching, draft temperature are 115 ℃, draw ratio is 3.5 times, again through cross directional stretch, draft temperature is 125 ℃, draw ratio is 7.5 times.All the other are identical with embodiment 1.
Embodiment 4, and 2. a kind of preparation method of porous film material, its step make the thick 450um of being of diaphragm material, and film is wide to be 1m.Its step 3. in thin-film sheet through two-way stretch, its first longitudinal stretching, draft temperature are 130 ℃, draw ratio is 5.0 times, again through cross directional stretch, draft temperature is 150 ℃, draw ratio is 10.0 times.All the other are identical with embodiment 1.
Embodiment 5, and 2. a kind of preparation method of porous film material, its step make the thick 200um of being of diaphragm material, and film is wide to be 0.2m.The step 3. longitudinal stretching temperature of the two-way stretch of middle thin-film sheet is 110 ℃, and draw ratio is 3.5 times, is 130 ℃ through the cross directional stretch temperature, and draw ratio is 8.5 times.All the other are identical with embodiment 1.
Embodiment 6, and 2. a kind of preparation method of porous film material, its step make the thick 350um of being of diaphragm material, and film is wide to be 0.6m.The step 3. longitudinal stretching temperature of the two-way stretch of middle thin-film sheet is 110 ℃, and draw ratio is 3.5 times, is 130 ℃ through the cross directional stretch temperature, and draw ratio is 8.5 times.All the other are identical with embodiment 1.
Embodiment 7, and 2. a kind of preparation method of porous film material, its step make the thick 500um of being of diaphragm material, and film is wide to be 1m.The step 3. longitudinal stretching temperature of the two-way stretch of middle thin-film sheet is 110 ℃, and draw ratio is 3.5 times, is 130 ℃ through the cross directional stretch temperature, and draw ratio is 8.5 times.All the other are identical with embodiment 1.
Embodiment 8, a kind of preparation method of porous film material, the blend composition that 1. 2. its step make step, extrude from die orifice, it by temperature 20 ℃ chilling roller, the sheet material that thickness is 500um is made in cooling, and more respectively by longitudinal stretching and cross directional stretch, making thickness is that 300um, width are the thin-film sheet of 0.2m.The thin-film sheet that 2. 3. step make step is through longitudinal stretching, and draft temperature is 90 ℃, and after draw ratio was 2.0 times of stretchings, again through cross directional stretch, draft temperature was 100 ℃, and draw ratio is 5.0 times.All the other are identical with embodiment 1.
Embodiment 9, a kind of preparation method of porous film material, the blend composition that 1. 2. its step make step, extrude from die orifice, it by temperature 40 ℃ chilling roller, the sheet material that thickness is 575um is made in cooling, and more respectively by longitudinal stretching and cross directional stretch, making thickness is that 375um, width are the thin-film sheet of 0.6m.The thin-film sheet that 2. 3. step make step is through longitudinal stretching, and draft temperature is 110 ℃, and after draw ratio was 3.5 times of stretchings, again through cross directional stretch, draft temperature was 125 ℃, and draw ratio is 7.5 times.All the other are identical with embodiment 1.
Embodiment 10, a kind of preparation method of porous film material, the blend composition that 1. 2. its step make step, extrude from die orifice, it by temperature 60 ℃ chilling roller, the sheet material that thickness is 650um is made in cooling, and more respectively by longitudinal stretching and cross directional stretch, making thickness is that 450um, width are the thin-film sheet of 1m.The thin-film sheet that 2. 3. step make step is through longitudinal stretching, and draft temperature is 130 ℃, and after draw ratio was 5 times of stretchings, again through cross directional stretch, draft temperature was 150 ℃, and draw ratio is 10 times.All the other are identical with embodiment 1.
Embodiment 11, a kind of preparation method of porous film material, the blend composition that 1. 2. its step make step, extrude from die orifice, it by temperature 40 ℃ chilling roller, the sheet material that thickness is 0.5mm is made in cooling, and more respectively by longitudinal stretching and cross directional stretch, making thickness is that 375um, width are the thin-film sheet of 0.6m.The thin-film sheet that 2. 3. step make step is through longitudinal stretching, and draft temperature is 110 ℃, and after draw ratio was 3.5 times of stretchings, again through cross directional stretch, draft temperature was 130 ℃, and draw ratio is 5.5 times.All the other are identical with embodiment 1.
Embodiment 12, a kind of preparation method of porous film material, its difference from Example 1 is that its blend composition is to be pressed 60% weight percent by external phase resin material PP (polypropylene), separation phase resin material LDPE (new LDPE (film grade)) and PA6 (nylon 6) press 10% and 30% the white proportion by subtraction of weight respectively, and other auxiliary agent oxidation inhibitor is by 1% weight percent uniform mixing and get, and other and embodiment 1 are same.
Embodiment 13, a kind of preparation method of porous film material, its difference from Example 1 be its blend composition by external phase resin material PP (polypropylene) by 75% weight percent, separate phase resin material LDPE (new LDPE (film grade)) by 25% and the white proportion by subtraction of weight, and other auxiliary agent oxidation inhibitor is by 1% weight percent uniform mixing and get, and other and embodiment 1 are same.
Embodiment 14, a kind of preparation method of porous film material, its difference from Example 1 be its blend composition by external phase resin material LLDPE (LLDPE) by 70% weight percent, separation phase resin material PP (polypropylene) and HDPE (high density polyethylene(HDPE)) press 20% and 10% the white proportion by subtraction of weight respectively, and other auxiliary agent oxidation inhibitor is by 1% weight percent uniform mixing and get, and other and embodiment 1 are same.
Embodiment 15, a kind of preparation method of porous film material, its difference from Example 1 be its blend composition by external phase resin material PP (polypropylene) by 80% weight percent, separation phase resin material PS (polystyrene) presses 20% the white proportion by subtraction of weight respectively, and other auxiliary agent oxidation inhibitor is by 1% weight percent uniform mixing and get, and other and embodiment 1 are same.
Embodiment 16, a kind of preparation method of porous film material, its difference from Example 1 be its blend composition by external phase resin material HDPE (high density polyethylene(HDPE)) by 50% weight percent, separation phase resin material LLDPE (LLDPE) and PS (polystyrene) press 10% and 40% the white proportion by subtraction of weight respectively, and other auxiliary agent oxidation inhibitor is by 1% weight percent uniform mixing and get, and other and embodiment 1 are same.
Claims (3)
1. the preparation method of a porous film material comprises the step of following order:
1. with external phase resin material 50%～90%, separate phase resin material 10%～50%, and other 0%～2.5% even mixing of auxiliary agent, all components sum is 100%, makes blend composition;
2. the blend composition of gained being made thick is 300～450 μ m, and width is 0.2～1m thin-film sheet;
3. the processing that is separated stretches the thin-film sheet that makes, promptly to the thin-film sheet longitudinal stretching, draft temperature is 90～130 ℃, draw ratio is 2.0～5.0 times, and cross directional stretch, draft temperature are 100～150 ℃, draw ratio is 5.0～10.0 times, the molecule that makes the external phase resin material in the sheet material with separate mutually the intermolecular junction of resin material and rupture, produce the gap, thereby prepare porous film material.
2. the preparation method of porous film material according to claim 1, it is characterized in that: the blend composition that 1. 2. step make step, extrude from die orifice, it by temperature 20～60 ℃ chilling roller, the sheet material that thickness is 500～650 μ m is made in cooling earlier, respectively by longitudinal stretching and cross directional stretch, making thickness is that 300～450 μ m, width are the thin-film sheet of 0.2～1m again.
3. the preparation method of porous film material according to claim 1, it is characterized in that: the blend composition that 1. 2. step make step, extrude from die orifice, it by temperature 20～60 ℃ chilling roller, the sheet material that thickness is 0.5mm is made in cooling, respectively by longitudinal stretching and cross directional stretch, making thickness is that 300～450um, width are the thin-film sheet of 0.2～1m again; The step 3. draft temperature of longitudinal stretching is 110 ℃, after draw ratio is 3.5 times of stretchings, is 130 ℃ through the draft temperature of cross directional stretch, and draw ratio is 5.5 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100282500A CN101280085B (en) | 2008-05-23 | 2008-05-23 | Preparation of porous film material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100282500A CN101280085B (en) | 2008-05-23 | 2008-05-23 | Preparation of porous film material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101280085A CN101280085A (en) | 2008-10-08 |
| CN101280085B true CN101280085B (en) | 2011-05-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100282500A Expired - Fee Related CN101280085B (en) | 2008-05-23 | 2008-05-23 | Preparation of porous film material |
Country Status (1)
| Country | Link |
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| CN (1) | CN101280085B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102922849B (en) * | 2012-11-08 | 2015-02-25 | 温州市金田塑业有限公司 | Biaxially-oriented polypropylene (BOPP) ventilated water-blocking membrane and preparation method thereof |
| CN104124412A (en) * | 2013-04-25 | 2014-10-29 | 河南天恩太阳能科技有限公司 | Dry unidirectional stretching method for manufacturing lithium battery diaphragm |
| CN115149205A (en) * | 2022-06-23 | 2022-10-04 | 中材锂膜(宁乡)有限公司 | Wet method lithium battery diaphragm preparation method and system based on film blowing process |
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| CN101280085A (en) | 2008-10-08 |
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Address after: Chancheng District of Guangdong city in Foshan province 528000 quarter of Huayi Road No. 28, a two building 17 layer (residence declaration) Patentee after: Foshan Jinhui Gao Ke photoelectric material Limited by Share Ltd. Address before: 528000 Chancheng City, Foshan Province Light District, No. three road, No. 7, No. Patentee before: FOSHAN JINHUI HIGH-TECH OPTOELECTRONIC MATERIAL Co.,Ltd. |
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