CN102672951B - Preparation method of unilateral drawing uniform adjustable micro-pore structure high temperature resistant diaphragm - Google Patents
Preparation method of unilateral drawing uniform adjustable micro-pore structure high temperature resistant diaphragm Download PDFInfo
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- CN102672951B CN102672951B CN201210130935.2A CN201210130935A CN102672951B CN 102672951 B CN102672951 B CN 102672951B CN 201210130935 A CN201210130935 A CN 201210130935A CN 102672951 B CN102672951 B CN 102672951B
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- preparation
- temperature
- diaphragm
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000011148 porous material Substances 0.000 title abstract description 9
- 229920000098 polyolefin Polymers 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000010345 tape casting Methods 0.000 claims abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 57
- 210000002469 basement membrane Anatomy 0.000 claims description 21
- 210000004379 membrane Anatomy 0.000 claims description 14
- 239000012528 membrane Substances 0.000 claims description 14
- 230000007547 defect Effects 0.000 claims description 8
- 239000012982 microporous membrane Substances 0.000 claims description 5
- 238000004513 sizing Methods 0.000 claims description 5
- 238000005987 sulfurization reaction Methods 0.000 claims description 5
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- 238000002203 pretreatment Methods 0.000 abstract 1
- -1 Polypropylene Polymers 0.000 description 13
- 239000004743 Polypropylene Substances 0.000 description 13
- 229920001155 polypropylene Polymers 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000002808 connective tissue Anatomy 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 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
Abstract
The invention discloses a preparation method of a unilateral drawing uniform adjustable micro-pore structure high temperature resistant diaphragm. The preparation method includes the following steps: (1) conducting surface pre-treatment on nanometer aluminum oxide in tetra-isopropyl-di-titanium-acid-ester; (2) evenly mixing pretreated nanometer aluminum oxide into polymer with the adding quantity occupying 0.5%-2.5% of that of the polymer, melting raw materials and adopting a tape casting method to prepare a base diaphragm; (3) drawing the base diaphragm under the condition that temperature is 10-155 DEG C, drawing speed is 0.1-30m/min, and drawing ratio is 1-3 times to form a micro-pore structure; (4) conducting re-drawing on the micro-pore diaphragm with the drawing ratio as 0.5-1.5 and conducting formation at the temperature of 70-165 DEG C to form a polyolefin micro-pore diaphragm product. The polyolefin micro-pore diaphragm product is even and adjustable in hole and reduces heat shrinkage rate.
Description
Technical field
The present invention relates to the preparation method of the even adjustable micro porous structure high-temperature-resistant membrane of a kind of simple tension, belong to polyalkene diaphragm technical field.
Background technology
Polypropylene diaphragm is the membrane manufacture that a kind of hot strength is high, resistance to elevated temperatures is good, is widely used in industrial production, such as lithium battery diaphragm.This membrane manufacture needs to have the ability hindering electrical conductivity, prior art normally adds inorganic particulate material in polypropylene material, as titanium dioxide and earth silicon material, the ability that can reduce inside battery electric leakage under battery normal condition is general, then easily both positive and negative polarity short circuit occurs under the emergency running into high temperature or ambient pressure at battery.Reason is that above-mentioned inorganic particulate is generally distributed in membrane surface, is not mixed into barrier film inside, easily comes off in use.
In addition, existing polypropylene diaphragm hole is uneven, due to polypropylene diaphragm mainly customed product, can be made into the product of different aperture according to different using function.Micro-pore septum be generally barrier film hole at nano level product, if hole is uneven, then at high temperature easily shrink, cause membrane manufacture mechanical property to decline, stability is not high.
Summary of the invention
The invention provides the even adjustable micro porous structure high-temperature-resistant membrane of a kind of simple tension, make product microcellular structure even, and can adjust, greatly reduce barrier film percent thermal shrinkage, improve the quality of products.
The present invention is realized by following technical scheme:
A preparation method for the even adjustable micro porous structure high-temperature-resistant membrane of simple tension is realized by following step:
(1) nano aluminium oxide is carried out surface preparation in tetra isopropyl two titanate esters, be specially and tetra isopropyl two titanate esters of 1 ~ 4% of described nano aluminium oxide quality and polypropylene are mixed with nano aluminium oxide, sulfuration 20min under 120 ~ 145 DEG C of conditions, then under 150 DEG C of conditions post-cure 3h;
(2) be evenly mixed in polymer by pretreated nano aluminium oxide, addition is 0.5% ~ 2.5% of polymer quality, carries out melting to raw material, adopts the tape casting to make basement membrane, and the basement membrane made is through 70 ~ 155 DEG C, and 10min ~ 30h anneals;
(3) by basement membrane 10 ~ 155 DEG C, draw speed is 0.1 ~ 30m/min, draw ratio is carry out stretching under the condition of 1 ~ 3 times to form microcellular structure;
(4) microporous membrane redraws, and draw ratio is 0.5 ~ 1.5,70 ~ 165 DEG C of sizing 1min ~ 10h, forms MIcroporous polyolefin film product.
In described step (2), melt temperature is 190 ~ 270 DEG C.The present invention through pretreated nano aluminium oxide and mixed with polymers, but not is covered in its surface after polymer film forming.
Stretch in described step (3) and be specially: first at 10 ~ 100 DEG C, draw ratio is carry out cold stretch under the condition of 1 ~ 3 times, till forming crazing defect; Then at 100 ~ 155 DEG C, draw ratio is stretch further under the condition of 1 ~ 3 times to form microcellular structure.
The micropore of the microcellular structure in described step (3) is 10nm ~ 30nm.
Beneficial effect of the present invention is:
1, inorganic particulate difficult drop-off, strengthens the stability of barrier film;
2, the mechanical property of separator product is strengthened;
3, production cost reduces.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
Adopt 100Kg polypropylene as raw material.
(1) get nano aluminium oxide 1Kg, get 25g tetra isopropyl two titanate esters and add in above-mentioned nano aluminium oxide, be uniformly mixed, put into heating kettle, control temperature between 120 ~ 145 DEG C, sulfuration 20min, then under control temperature is 150 DEG C of conditions post-cure 3h;
(2) getting above-mentioned pretreated nano aluminium oxide 0.8Kg is evenly mixed in complete 100Kg polypropylene, melting is carried out to above-mentioned mixed material, melt temperature is 190 ~ 270 DEG C, the tape casting is adopted to make basement membrane, the basement membrane made is through control temperature at 70 ~ 155 DEG C, and 10min ~ 30h anneals;
(3) be that 1 times of condition is constant by above-mentioned basement membrane restrained stretching ratio, control cold stretch under 20 DEG C of conditions, basement membrane forms crazing defect gradually, continues to stretch, until basement membrane forms uniform crazing defect; Then stretch further under 100 ~ 125 DEG C of conditions and form microcellular structure, ensure that micropore stops at 10nm;
(4) above-mentioned microporous membrane redraws, and draw ratio is 0.5, and control temperature, at 70 ~ 100 DEG C of sizing 10min, forms MIcroporous polyolefin film product.
Embodiment 2
Adopt 100Kg polypropylene as raw material.
(1) get nano aluminium oxide 3Kg, get 40g tetra isopropyl two titanate esters and add in above-mentioned nano aluminium oxide, be uniformly mixed, put into heating kettle, control temperature between 120 ~ 145 DEG C, sulfuration 20min, then under control temperature is 150 DEG C of conditions post-cure 3h;
(2) getting above-mentioned pretreated nano aluminium oxide 2.3Kg is evenly mixed in complete 100Kg polypropylene, melting is carried out to above-mentioned mixed material, melt temperature is 190 ~ 270 DEG C, the tape casting is adopted to make basement membrane, the basement membrane made is through control temperature at 70 ~ 155 DEG C, and 10min ~ 30h anneals;
(3) be that 3 times of conditions are constant by above-mentioned basement membrane restrained stretching ratio, control cold stretch under 85 DEG C of conditions, basement membrane forms crazing defect gradually, continues to stretch, until basement membrane forms uniform crazing defect; Then stretch further under 120 ~ 150 DEG C of conditions and form microcellular structure, ensure that micropore stops at 28nm;
(4) above-mentioned microporous membrane redraws, and draw ratio is 1.0, and control temperature, at 100 ~ 150 DEG C of sizing 8 ~ 10h, forms MIcroporous polyolefin film product.
Embodiment 3
Adopt 100Kg polypropylene as raw material.
(1) get nano aluminium oxide 2Kg, get 20g tetra isopropyl two titanate esters and add in above-mentioned nano aluminium oxide, be uniformly mixed, put into heating kettle, control temperature between 120 ~ 145 DEG C, sulfuration 20min, then under control temperature is 150 DEG C of conditions post-cure 3h;
(2) getting above-mentioned pretreated nano aluminium oxide 1.8Kg is evenly mixed in complete 100Kg polypropylene, melting is carried out to above-mentioned mixed material, melt temperature is 190 ~ 270 DEG C, the tape casting is adopted to make basement membrane, the basement membrane made is through control temperature at 70 ~ 155 DEG C, and 10min ~ 30h anneals;
(3) be that 2 times of conditions are constant by above-mentioned basement membrane restrained stretching ratio, control cold stretch under 55 DEG C of conditions, basement membrane forms crazing defect gradually, continues to stretch, until basement membrane forms uniform crazing defect; Then stretch further under 130 DEG C of conditions and form microcellular structure, ensure that micropore stops at 21nm;
(4) above-mentioned microporous membrane redraws, and draw ratio is 1.5, and control temperature, at 85 ~ 105 DEG C of sizing 4 ~ 6h, forms MIcroporous polyolefin film product.
The micropore of the micro-pore septum goods that the present invention produces, between 10 ~ 30nm, when the polypropylene diaphragm that a small amount of nano aluminium oxide of interpolation is made, can make the less membrane manufacture of micro-pore diameter at a lower temperature; When adding nano oxidized aluminum amount and being larger, polypropylene diaphragm can improve makes temperature, and the micropore of membrane manufacture also can reach 30nm, and its mechanical strength is higher.
Adopt barrier film of the present invention as the product of battery adventitia, there is the ability of more excellent obstruction electrical conductivity, inside battery electric leakage can be reduced under battery normal condition, both positive and negative polarity short circuit can be stoped under the emergency that battery runs into high temperature or ambient pressure.
Claims (4)
1. a preparation method for the even adjustable micro porous structure high-temperature-resistant membrane of simple tension, it is characterized in that by following step realize:
(1) nano aluminium oxide is carried out surface preparation in tetra isopropyl titanate, be specially and the tetra isopropyl titanate of 1 ~ 4% of described nano aluminium oxide quality is mixed with nano aluminium oxide, sulfuration 20min under 120 ~ 145 DEG C of conditions, then under 150 DEG C of conditions post-cure 3h;
(2) be evenly mixed in polymer by pretreated nano aluminium oxide, addition is 0.5% ~ 2.5% of polymer quality, carries out melting to raw material, adopts the tape casting to make basement membrane, and the basement membrane made is through 70 ~ 155 DEG C, and 10min ~ 30h anneals;
(3) by basement membrane 10 ~ 155 DEG C, draw speed is 0.1 ~ 30m/min, draw ratio is carry out stretching under the condition of 1 ~ 3 times to form microcellular structure;
(4) microporous membrane redraws, and draw ratio is 0.5 ~ 1.5,70 ~ 165 DEG C of sizing 1min ~ 10h, forms MIcroporous polyolefin film product.
2. the preparation method of the even adjustable micro porous structure high-temperature-resistant membrane of simple tension as claimed in claim 1, is characterized in that in described step (2), melt temperature is 190 ~ 270 DEG C.
3. the preparation method of the even adjustable micro porous structure high-temperature-resistant membrane of simple tension as claimed in claim 1, it is characterized in that stretches in described step (3) is specially: first at 10 ~ 100 DEG C, draw ratio is carry out cold stretch under the condition of 1 ~ 3 times, till forming crazing defect; Then at 100 ~ 155 DEG C, draw ratio is stretch further under the condition of 1 ~ 3 times to form microcellular structure.
4. the preparation method of the even adjustable micro porous structure high-temperature-resistant membrane of simple tension as claimed in claim 1, is characterized in that the micropore of the microcellular structure in described step (3) is 10nm ~ 30nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210130935.2A CN102672951B (en) | 2012-04-27 | 2012-04-27 | Preparation method of unilateral drawing uniform adjustable micro-pore structure high temperature resistant diaphragm |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210130935.2A CN102672951B (en) | 2012-04-27 | 2012-04-27 | Preparation method of unilateral drawing uniform adjustable micro-pore structure high temperature resistant diaphragm |
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| Publication Number | Publication Date |
|---|---|
| CN102672951A CN102672951A (en) | 2012-09-19 |
| CN102672951B true CN102672951B (en) | 2015-05-20 |
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| CN201210130935.2A Expired - Fee Related CN102672951B (en) | 2012-04-27 | 2012-04-27 | Preparation method of unilateral drawing uniform adjustable micro-pore structure high temperature resistant diaphragm |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101710614A (en) * | 2009-12-16 | 2010-05-19 | 南京大学 | Diaphragm of modified lithium battery with medium hole nano particles |
| CN101798183A (en) * | 2010-04-09 | 2010-08-11 | 上海交通大学 | Preparation method of Al-Doped ZnO film |
| CN102064299A (en) * | 2010-12-25 | 2011-05-18 | 佛山塑料集团股份有限公司 | Polyolefin multi-layer porous diaphragm for lithium ion battery and preparation method thereof |
| JP2011233519A (en) * | 2010-04-09 | 2011-11-17 | Kawaken Fine Chemicals Co Ltd | Separator for nonaqueous electrolyte battery, and lithium ion secondary battery |
-
2012
- 2012-04-27 CN CN201210130935.2A patent/CN102672951B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101710614A (en) * | 2009-12-16 | 2010-05-19 | 南京大学 | Diaphragm of modified lithium battery with medium hole nano particles |
| CN101798183A (en) * | 2010-04-09 | 2010-08-11 | 上海交通大学 | Preparation method of Al-Doped ZnO film |
| JP2011233519A (en) * | 2010-04-09 | 2011-11-17 | Kawaken Fine Chemicals Co Ltd | Separator for nonaqueous electrolyte battery, and lithium ion secondary battery |
| CN102064299A (en) * | 2010-12-25 | 2011-05-18 | 佛山塑料集团股份有限公司 | Polyolefin multi-layer porous diaphragm for lithium ion battery and preparation method thereof |
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| CN102672951A (en) | 2012-09-19 |
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