CN103178230A - Production method of lithium ion battery separation film - Google Patents
Production method of lithium ion battery separation film Download PDFInfo
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- CN103178230A CN103178230A CN2013100711009A CN201310071100A CN103178230A CN 103178230 A CN103178230 A CN 103178230A CN 2013100711009 A CN2013100711009 A CN 2013100711009A CN 201310071100 A CN201310071100 A CN 201310071100A CN 103178230 A CN103178230 A CN 103178230A
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- lithium ion
- ion battery
- polyphenylene sulfide
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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 invention discloses a production method of a lithium ion battery separation film. The method comprises the steps that: polyphenylene sulfide is subjected to melt extrusion, wherein an extrusion die head slit width is 5-500 micrometers; extruded polyphenylene sulfide is processed by using a cooling roll, such that a cast film is formed; the polyphenylene sulfide cast film is drawn, and heat setting is carried out. According to the invention, polyphenylene sulfide is extruded, and is drawn under a preset temperature; a drawing ratio is controlled, such that a micro-pore average size regulating effect is achieved. With the method, the thickness of producible lithium ion battery separation film is reduced, resource is effectively saved, lithium ion battery separation film breakage temperature is increased, and lithium ion battery separation film safety is improved.
Description
[technical field]
The present invention relates to lithium ion battery separator, relate in particular to a kind of production method of lithium ion battery separator.
[background technology]
The mechanism of stretching pore-forming technique is for being in the hypocrystalline state when polymer, and when inside existed crystal region and noncrystalline domain, the mechanical property of crystal region and noncrystalline domain was different.When polymer was subject to tensile force, noncrystalline domain was subject to excessively stretching and local fracture forms micropore, and crystal region is kept as the skeleton in micropore district.
(the research of polyphenylene sulfide hollow fiber microfiltration membrane such as Wang Lihua, textile journal 25(1), 25-27) has been studied the pore-forming performance impact of drawing process to the PPS doughnut, such hollow-fibre membrane can be used as filter membrane and uses, but can not make the barrier film of lithium ion battery.
Application number provides a kind of novel lithium ion battery diaphragm and production method thereof for 03126299.6 Chinese invention patent application, and this microporous barrier can be used for lithium ion battery separator.But because the material that uses is polyolefin, so broken film temperature is very low, lower than 160 ℃.The barrier film percent thermal shrinkage that polyolefine material is done is very high, stretched after, percent thermal shrinkage can be higher, 120 ℃ of constant temperature 1 hour, polyalkene diaphragm surpassed 3% at the percent thermal shrinkage of draw direction, and percent thermal shrinkage is too high, fail safe to lithium ion battery is unfavorable, easily causes short circuit.
[summary of the invention]
The technical problem to be solved in the present invention is to provide the production method of a kind of thin thickness, broken film temperature is high, percent thermal shrinkage is low lithium ion battery separator.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is that a kind of production method of lithium ion battery separator comprises the following steps:
101) polyphenylene sulfide is through melt extruding, and the slit width of extrusion die is the 5-500 micron, and the polyphenylene sulfide of extruding forms casting films through chill roll;
102) carry out again thermal finalization after the polyphenylene sulfide casting films stretches.
The production method of above-described lithium ion battery separator, in step 101, extrusion temperature is 260--400 ℃, the chill roll surface temperature is 20-100 ℃.
The production method of above-described lithium ion battery separator in step 102, stretches casting films in 50-280 ℃ of scope, carry out when unidirectional, and the draw ratio of stretching is less than 10; When carrying out biaxial tension, the draw ratio of cross directional stretch is less than 8, and the draw ratio of longitudinal stretching is less than 10.
The production method of above-described lithium ion battery separator, heat setting temperature are 200-280 ℃, shaping time 0.1-30 minute.
The production method of above-described lithium ion battery separator is before step 102, with casting films constant temperature in 50-280 ℃ of scope, constant temperature time 1-30 minute.
The present invention extrudes polyphenylene sulfide, stretches under preset temperature, and restrained stretching is than reaching the effect of regulating the micropore average pore size; The present invention has reduced the thickness of producible lithium ion battery separator, has effectively saved resource, has improved the broken film temperature of lithium ion battery separator, has improved the fail safe of lithium ion battery separator.
[embodiment]
The present invention is further detailed explanation below by embodiment.
The production method of the ultra-thin polyphenylene sulfide barrier film of the present invention is:
(1) polyphenylene sulfide is through melt extruding, and extrusion temperature is 260-400 ℃, and the slit width of extrusion die is the 5-500 micron.
(2) extrude by the supercooling roller, the chill roll surface temperature control is 20-100 ℃, forms casting films.
(3) with casting films constant temperature in 50-280 ℃ of scope, constant temperature time is 1 minute-30 minutes.
(4) PPS (polyphenylene sulfide) films after constant temperature is stretched, if simple tension, draw ratio is less than 10; If biaxial tension, the draw ratio of cross directional stretch is less than 8, and the draw ratio of longitudinal stretching is less than 10, and the minimum stretch ratio is not less than 1.5.
(5) heat setting temperature is 200 ℃ to 280 ℃, shaping time 0.1-30 minute.
The polyphenylene sulfide microporous barrier aperture that obtains is that the 50-500 nanometer is controlled, and thickness is the 0.5-50 micron, and less than 1%, broken film temperature is 280 ℃ to percent thermal shrinkage (120 ℃ constant temperature 1 hour).
Embodiment 1,
(1) the polyphenylene sulfide particle melt extrudes through the extrusion die of film biaxial orientation stretching machine, and extrusion temperature is 300 ℃, and the slit width of extrusion die is 20 microns.
(2) extrude by the supercooling roller, the chill roll surface temperature control is 20 ℃, forms casting films.
(3) with casting films at 80 ℃ of constant temperature, constant temperature time is 5 minutes.
(4) send into the PPS (polyphenylene sulfide) films after constant temperature in length and breadth that biaxial orientation stretching machine stretches, the draw ratio of cross directional stretch is 5, and the draw ratio of longitudinal stretching is 8.
(5) carry out thermal finalization after the polyphenylene sulfide rolling after stretching in insulating box, heat setting temperature is 230 ℃, and shaping time 5 minutes obtains the lithium ion battery micro-pore septum.
After testing, the polyphenylene sulfide microporous barrier average pore size that obtains is 80 nanometers, and thickness is 0.5 micron, percent thermal shrinkage (120 ℃ constant temperature 1 hour) 0.08%, and broken film temperature is 280 ℃.
Embodiment 2,
(1) the polyphenylene sulfide particle melt extrudes through the extrusion die of film biaxial orientation stretching machine, and extrusion temperature is 380 ℃, and the slit width of extrusion die is 100 microns.
(2) extrude by the supercooling roller, the chill roll surface temperature control is 80 ℃, forms casting films.
(3) with casting films at 50 ℃ of constant temperature, constant temperature time is 10 minutes.
(4) PPS (polyphenylene sulfide) films after constant temperature is stretched, the draw ratio of cross directional stretch is 6, and the draw ratio of longitudinal stretching is 9.
(5) carry out thermal finalization after the polyphenylene sulfide rolling after stretching in insulating box, heat setting temperature is 260 ℃, and shaping time 15 minutes obtains the lithium ion battery micro-pore septum.
After testing, the polyphenylene sulfide microporous barrier average pore size that obtains is 120 nanometers, and thickness is 2 microns, percent thermal shrinkage (120 ℃ constant temperature 1 hour) 0.09%, and broken film temperature is 280 ℃.
Embodiment 3,
(1) the polyphenylene sulfide particle melt extrudes through the extrusion die of film biaxial orientation stretching machine, and extrusion temperature is 320 ℃, and the slit width of extrusion die is 30 microns.
(2) extrude by the supercooling roller, the chill roll surface temperature control is 30 ℃, forms casting films.
(3) with casting films at 70 ℃ of constant temperature, constant temperature time is 15 minutes.
(4) PPS (polyphenylene sulfide) films after constant temperature is stretched, the draw ratio of cross directional stretch is 4, and the draw ratio of longitudinal stretching is 8.
(5) carry out thermal finalization after the polyphenylene sulfide rolling after stretching in insulating box, heat setting temperature is 200 ℃, and shaping time 20 minutes obtains the lithium ion battery micro-pore septum.
After testing, the polyphenylene sulfide microporous barrier average pore size that obtains is 70 nanometers, and thickness is 1 micron, percent thermal shrinkage (120 ℃ constant temperature 1 hour) 0.07%, and broken film temperature is 280 ℃.
Embodiment 4,
(1) the polyphenylene sulfide particle melt extrudes through the extrusion die of film biaxial orientation stretching machine, and extrusion temperature is 310 ℃, and the slit width of extrusion die is 20 microns.
(2) extrude by the supercooling roller, the chill roll surface temperature control is 30 ℃, forms casting films.
(3) with casting films at 60 ℃ of constant temperature, constant temperature time is 15 minutes.
(4) PPS (polyphenylene sulfide) films after constant temperature is carried out longitudinal stretching, draw ratio is 6.
(5) carry out thermal finalization after the polyphenylene sulfide rolling after stretching in insulating box, heat setting temperature is 200 ℃, and shaping time 10 minutes obtains the lithium ion battery micro-pore septum.
After testing, the polyphenylene sulfide microporous barrier average pore size that obtains is 50 nanometers, and thickness is 3 microns, percent thermal shrinkage (120 ℃ constant temperature 1 hour) 0.06%, and broken film temperature is 280 ℃.The present invention extrudes polyphenylene sulfide, stretches under preset temperature, and restrained stretching is than reaching the effect of regulating the micropore average pore size; The present invention has reduced the thickness of producible lithium ion battery separator, has effectively saved resource; The present invention has improved the broken film temperature of lithium ion secondary battery membrane, has improved the security performance of lithium ion secondary battery membrane.
Claims (5)
1. the production method of a lithium ion battery separator, is characterized in that, comprises the following steps:
101) polyphenylene sulfide is through melt extruding, and the slit width of extrusion die is the 5-500 micron, and the polyphenylene sulfide of extruding forms casting films through chill roll;
102) carry out again thermal finalization after the polyphenylene sulfide casting films stretches.
2. the production method of lithium ion battery separator according to claim 1, is characterized in that, in step 101, extrusion temperature is 260--400 ℃, and the chill roll surface temperature is 20-100 ℃.
3. the production method of lithium ion battery separator according to claim 1, is characterized in that, in step 102, casting films stretched in 50-280 ℃ of scope, carries out when unidirectional, and the draw ratio of stretching is less than 10; When carrying out biaxial tension, the draw ratio of cross directional stretch is less than 8, and the draw ratio of longitudinal stretching is less than 10.
4. the production method of lithium ion battery separator according to claim 1, is characterized in that, heat setting temperature is 200-280 ℃, shaping time 0.1-30 minute.
5. the production method of lithium ion battery separator according to claim 1, is characterized in that, before step 102, with casting films constant temperature in 50-280 ℃ of scope, constant temperature time 1-30 minute.
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| CN2013100711009A CN103178230A (en) | 2013-03-06 | 2013-03-06 | Production method of lithium ion battery separation film |
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| CN2013100711009A CN103178230A (en) | 2013-03-06 | 2013-03-06 | Production method of lithium ion battery separation film |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106554620A (en) * | 2016-11-24 | 2017-04-05 | 扬州亚宝新材料科技有限公司 | A kind of PPS films and preparation method thereof |
| CN106584878A (en) * | 2016-11-23 | 2017-04-26 | 广东工业大学 | Polyphenylene sulfide microporous membrane containing lamella structure and preparation method thereof |
| CN111477876A (en) * | 2019-01-24 | 2020-07-31 | 东丽先端材料研究开发（中国）有限公司 | Multilayer film, current collector, pole piece and battery |
| CN112310557A (en) * | 2020-11-03 | 2021-02-02 | 天津工业大学 | Preparation method of polyphenylene sulfide-based diaphragm based on viscous flow modification technology |
| CN115084778A (en) * | 2022-08-23 | 2022-09-20 | 四川中科兴业高新材料有限公司 | Battery diaphragm produced by polyphenylene sulfide and method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101797800A (en) * | 2009-12-30 | 2010-08-11 | 四川华通特种工程塑料研究中心有限公司 | Technology for preparing polyphenyl sulfide composite film |
| CN102001186A (en) * | 2010-10-13 | 2011-04-06 | 深圳市星源材质科技股份有限公司 | Method for forming polyolefin microporous membrane and application thereof |
| CN102751460A (en) * | 2012-05-23 | 2012-10-24 | 杭州福膜新材料科技有限公司 | High-temperature-resisting composite isolation film and preparation method thereof |
-
2013
- 2013-03-06 CN CN2013100711009A patent/CN103178230A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101797800A (en) * | 2009-12-30 | 2010-08-11 | 四川华通特种工程塑料研究中心有限公司 | Technology for preparing polyphenyl sulfide composite film |
| CN102001186A (en) * | 2010-10-13 | 2011-04-06 | 深圳市星源材质科技股份有限公司 | Method for forming polyolefin microporous membrane and application thereof |
| CN102751460A (en) * | 2012-05-23 | 2012-10-24 | 杭州福膜新材料科技有限公司 | High-temperature-resisting composite isolation film and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106584878A (en) * | 2016-11-23 | 2017-04-26 | 广东工业大学 | Polyphenylene sulfide microporous membrane containing lamella structure and preparation method thereof |
| CN106554620A (en) * | 2016-11-24 | 2017-04-05 | 扬州亚宝新材料科技有限公司 | A kind of PPS films and preparation method thereof |
| CN111477876A (en) * | 2019-01-24 | 2020-07-31 | 东丽先端材料研究开发（中国）有限公司 | Multilayer film, current collector, pole piece and battery |
| CN112310557A (en) * | 2020-11-03 | 2021-02-02 | 天津工业大学 | Preparation method of polyphenylene sulfide-based diaphragm based on viscous flow modification technology |
| CN112310557B (en) * | 2020-11-03 | 2022-12-23 | 天津工业大学 | Preparation method of polyphenylene sulfide-based diaphragm based on viscous flow modification technology |
| CN115084778A (en) * | 2022-08-23 | 2022-09-20 | 四川中科兴业高新材料有限公司 | Battery diaphragm produced by polyphenylene sulfide and method |
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Application publication date: 20130626 |