CN104086797A - Preparation method of high-melting-point resin composite diaphragm - Google Patents
Preparation method of high-melting-point resin composite diaphragm Download PDFInfo
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- CN104086797A CN104086797A CN201410288030.7A CN201410288030A CN104086797A CN 104086797 A CN104086797 A CN 104086797A CN 201410288030 A CN201410288030 A CN 201410288030A CN 104086797 A CN104086797 A CN 104086797A
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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 relates to a preparation method of a high-melting-point resin composite diaphragm, which is characterized by comprising the following steps: adhering polymer particles or polymer particles and inorganic particles packing to the surface of a microporous diaphragm, spraying an adhesive and drying and rolling to form a composite diaphragm; dissolving the polymer diaphragm material in certain solvent to form homogenous slurry; uniformly dispersing the polymer particles or polymer particles and inorganic particles into the slurry; and finally loading the surface of the microporous diaphragm with the slurry to obtain the composite diaphragm. According to the diaphragm, the composite diaphragm is prepared by adhering polymer particles or polymer particles and inorganic particles packing to the surface of the microporous diaphragm, spraying the adhesive and drying and rolling; the adopted polymer particles are generally the superfine powder of high-melting-point engineering resin.
Description
Technical field
The present invention relates to a kind of resin with high melting point composite diaphragm preparation method, be applied to the barrier film of automobile power cell.Belong to technical field of new energies.
Background technology
Energy-conservation and the new-energy automobile such as hybrid electric vehicle, pure electric automobile and fuel-cell vehicle becomes reasonable evolutionary path.Yet safe reliability, life-span, continual mileage, cost and public facility etc. have greatly limited the fast development of new-energy automobile, this is wherein especially the most key with technological breakthrough and the mass-producing application of power cell.Lithium ion battery has that specific energy is high, operating voltage is high, self-discharge rate is little, advantages of environment protection, is new-energy automobile ideal power battery.But owing to using liquid electrolyte solution, make lithium ion battery have potential safety hazard, limited its large-scale promotion on automobile.As one of key part of barrier film lithium cell, the safety performance of battery is played an important role.
Barrier film between positive and negative electrode has electrolyte ion transmission path, prevents the effect of positive and negative electrode contact short circuit.Yet current used polyolefins barrier film melting closed porosity when battery temperature is too high, intercepts the transmission of electrolyte ion, reduces security risk; But because the resistance toheat of polyolefine itself is poor, along with the sharply rising of temperature, the protection that polyolefin polymers forms is destroyed, and loses defencive function; And after polyalkene diaphragm itself punctured by impurity (or Zhi Jing) etc., can make equally potential safety hazard sharply increase.
In order to change this because barrier film destroys the safety problem causing, people have carried out a series of research, on the one hand, to existing diagram modification, improve barrier film mechanical property and resistance toheat, for example membrane surface coating inorganic particle or polymkeric substance and inorganic particulate are made matrix material (US 8409746 B2 for example, EP 2528139 A2, EP 2528142 A2, US7691529 B2, US 20130065132 A1); On the other hand, higher with temperature resistant grade, the better polymkeric substance of mechanical property is prepared barrier film (for example publication number CN 101645497A, publication number CN 101420018A, application publication number CN 101752539 A, application publication number CN 101752540 A), as the polymer materials of barrier film itself, can there is the reaction (for example publication number US2012/0295154 A1) of similar closed pore effect, or add other polymkeric substance that can realize closed pore effect etc. (for example publication number CN 101656306A, publication number US2013/0022858 A1).
Summary of the invention
Object of the present invention is for existing septate shortcoming; a kind of resin with high melting point composite diaphragm preparation method is provided; this barrier film sprays sizing agent after by micro-pore septum surface attachment polymer beads or polymer beads and inorganic particulate filler; dryer roll swaging becomes composite diaphragm, and the polymer beads using is generally high-melting-point engineering resin ultrafine powder.
Technical solution of the present invention is achieved in that a kind of resin with high melting point composite diaphragm preparation method; it is characterized in that: after micro-pore septum surface attachment polymer beads or polymer beads and inorganic particulate filler, spray sizing agent; dryer roll swaging becomes composite diaphragm; be about to membrane for polymer material dissolves in certain solvent, form homogeneous slurry.Then dispersed polymer beads or polymer beads and inorganic particulate in slurry, slurry is finally loaded on to micro-pore septum surface, prepare composite diaphragm, its polymeric matrix adopts is that a kind of in polyvinylidene difluoride (PVDF), polyvinylidene difluoride (PVDF)-R 1216 or their combination quality are than 0～1/0～1; Filler used is 180 ℃ of above polymer beads of melt temperature, for polyetherketone, polyether-ether-ketone, polyether ether ketone ketone, a kind of in polyetherketoneetherketoneketone, polybenzothiozole, polybenzimidazole, polyphenylene sulfide or their combination quality be than 0～1/0～1, and described inorganic particulate is a kind of in silicon-dioxide, titanium dioxide, calcium oxide, barium titanate or their combination; Described micro-pore septum is a kind of in polypropylene diaphragm, polyethylene barrier film and polypropylene, polyethylene composite diaphragm.
Positively effect of the present invention is that composition polymer barrier film adopts polymer beads or polymkeric substance and inorganic particulate surperficial at micro-pore septum as filler adheres, and dryer roll swaging becomes composite diaphragm.The polymer beads adding or polymkeric substance and inorganic particulate have improved the mechanical property of barrier film, and the barrier film obtaining has higher porosity, is conducive to the diffusion transport of electrolyte ion; When internal temperature of battery continues to raise, the polymkeric substance of melting or polymkeric substance and inorganic particulate can further stop the transmission of electrolyte ion, reduce the chemical reaction of battery, the security that improves battery.
Accompanying drawing explanation
Fig. 1 is that the present invention prepares barrier film process schematic diagram.
Fig. 2 is that the barrier film heat of embodiments of the invention 1 preparation respectively heats the photo of 1h under 90 ℃, 135 ℃, 165 ℃ environment.
Embodiment
Below in conjunction with accompanying drawing, embodiments of the present invention are described, described embodiment is the specific descriptions to claim of the present invention just, and claim includes but not limited to described embodiment content.
Embodiment 1
(1) 7.5g polyvinylidene difluoride (PVDF)-R 1216 is dissolved in 48g acetone, through heating, strong stirring, after it fully dissolves, adds ultra-fine polyether-ether-ketone ketone powder 2.25g, continue heating, stir after 4～8h, obtain dispersed colloid mixed solution preferably; (2) in the colloid mixed solution in step (1), dropwise add the dehydrated alcohol of 6.0g as pore-creating agent, continue to stir; (3) the colloid mixed solution of step (2) is coated in to the two sides of micro-pore septum; (4) take off film by after its roll-in, at the temperature of 70 ℃, film is carried out to 1～2h vacuum drying.As can be seen from Figure 2, the polymer beads of interpolation has improved the resistance toheat of barrier film, and at 165 ℃, thermal contraction is 3%; As can be seen from Table 1, add after polymer beads, tensile strength is better.In conjunction with Fig. 2, table 1, can find out, add after polymer beads, the barrier film of preparation has good resistance toheat and mechanical property.
Embodiment 2
(1) 7.5g polyvinylidene difluoride (PVDF) is dissolved in 46g acetone, through heating, strong stirring, after it fully dissolves; (2) to (1), add ultra-fine polyether-ether-ketone powder 0.45g, continue heating, stir after for some time, obtain dispersed colloid mixed solution preferably; (3) the colloid mixed solution of step (2) is coated in to the two sides of micro-pore septum; (5) take off film by after its roll-in, at the temperature of 75 ℃, film is carried out to 2h vacuum drying.
Embodiment 3
(1) 7.5g polyvinylidene difluoride (PVDF)-R 1216 is dissolved in 48g acetone, through heating, strong stirring, after it fully dissolves, adds the mixture 1.35g of ultra-fine polyetherketone powder and ultra-fine polybenzimidazole powder, continue heating, stir; (2) in the colloid mixed solution in step (1), dropwise add the propyl carbinol of 5.0g as pore-creating agent, continue to stir; (3) the colloid mixed solution of step (2) is coated in to the two sides of micro-pore septum; (4) take off film by after its roll-in, at the temperature of 70 ℃, film is carried out to 1～2h vacuum drying.
Embodiment 4
(1) 7.5g polyvinylidene difluoride (PVDF)-R 1216 is dissolved in 48g NMP, through heating, strong stirring, after it fully dissolves, adds the mixture 0.45g of ultra-fine pps powder and ultra-fine polybenzimidazole powder, continue heating, stir; (2) in the colloid mixed solution in step (1), dropwise add the propyl carbinol of 5.0g as pore-creating agent, continue to stir; (3) micro-pore septum is by 2h in the colloid mixed solution of impregnation steps (2); (4). take off film by after its roll-in, at the temperature of 75 ℃, film is carried out to 1～2h vacuum drying.
Embodiment 5
(1) 7.5g polyvinylidene difluoride (PVDF) is dissolved in the acetone and NMP mixed solvent of 48g, through heating, strong stirring, after it fully dissolves, adds the mixture 1.125g of ultra-fine polyetherketoneetherketoneketone powder and ultra-fine polybenzothiozole powder, continue heating, stir; (2) in the colloid mixed solution in step (1), dropwise add the propyl carbinol of 4.5g as pore-creating agent, continue to stir; (3) the colloid mixed solution of step (2) is coated in to the two sides of micro-pore septum; (4) take off film by after its roll-in, at the temperature of 70 ℃, film is carried out to 2h vacuum drying.
Claims (4)
1. a resin with high melting point composite diaphragm preparation method, it is characterized in that: after micro-pore septum surface attachment polymer beads or polymer beads and inorganic particulate filler, spray sizing agent, dryer roll swaging becomes composite diaphragm, be about to membrane for polymer material dissolves in certain solvent, form homogeneous slurry, then dispersed polymer beads or polymer beads and inorganic particulate in slurry, slurry is finally loaded on to micro-pore septum surface, prepare composite diaphragm, what its polymeric matrix adopted is polyvinylidene difluoride (PVDF), a kind of in polyvinylidene difluoride (PVDF)-R 1216 or their combination quality are than 0～1/0～1.
2. the preparation method of a kind of resin with high melting point composite diaphragm according to claim 1, is characterized in that described filler is polymer beads; Filler is the above polymer beads of 180 ℃ of melt temperatures, is polyetherketone, polyether-ether-ketone, polyether ether ketone ketone, and a kind of in polyetherketoneetherketoneketone, polybenzothiozole, polybenzimidazole, polyphenylene sulfide or their combination quality are than 0～1/0～1.
3. the preparation method of a kind of resin with high melting point composite diaphragm according to claim 2, is characterized in that described inorganic particulate is a kind of in silicon-dioxide, titanium dioxide, calcium oxide, barium titanate or their combination.
4. according to claim 2, the preparation method of a kind of resin with high melting point composite diaphragm described in 3, is characterized in that described micro-pore septum is a kind of in polypropylene diaphragm, polyethylene barrier film and polypropylene, polyethylene composite diaphragm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410288030.7A CN104086797A (en) | 2014-06-25 | 2014-06-25 | Preparation method of high-melting-point resin composite diaphragm |
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| CN201410288030.7A CN104086797A (en) | 2014-06-25 | 2014-06-25 | Preparation method of high-melting-point resin composite diaphragm |
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| CN104086797A true CN104086797A (en) | 2014-10-08 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106159162A (en) * | 2016-08-31 | 2016-11-23 | 襄阳艾克特电池科技股份有限公司 | A kind of high-performance lithium battery diaphragm manufacture method |
| CN107732108A (en) * | 2017-10-09 | 2018-02-23 | 上海恩捷新材料科技股份有限公司 | A kind of electrochemical appliance barrier film and preparation method thereof |
| CN112194978A (en) * | 2020-08-25 | 2021-01-08 | 河北金力新能源科技股份有限公司 | High-heat-resistant coating slurry, high-temperature-resistant diaphragm for lithium battery and preparation method of high-temperature-resistant diaphragm |
| CN112259911A (en) * | 2020-09-30 | 2021-01-22 | 上海恩捷新材料科技有限公司 | Electrochemical device, novel non-woven fabric ceramic diaphragm and preparation method thereof |
-
2014
- 2014-06-25 CN CN201410288030.7A patent/CN104086797A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 徐玲妍: "纳米SiO2/PVdF-HFP复合PP无纺布基锂离子电池隔膜的制备与性能研究", 《中国优秀硕士学位论文全文数据库 工程科技II辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106159162A (en) * | 2016-08-31 | 2016-11-23 | 襄阳艾克特电池科技股份有限公司 | A kind of high-performance lithium battery diaphragm manufacture method |
| CN107732108A (en) * | 2017-10-09 | 2018-02-23 | 上海恩捷新材料科技股份有限公司 | A kind of electrochemical appliance barrier film and preparation method thereof |
| CN112194978A (en) * | 2020-08-25 | 2021-01-08 | 河北金力新能源科技股份有限公司 | High-heat-resistant coating slurry, high-temperature-resistant diaphragm for lithium battery and preparation method of high-temperature-resistant diaphragm |
| CN112259911A (en) * | 2020-09-30 | 2021-01-22 | 上海恩捷新材料科技有限公司 | Electrochemical device, novel non-woven fabric ceramic diaphragm and preparation method thereof |
| CN112259911B (en) * | 2020-09-30 | 2021-08-06 | 上海恩捷新材料科技有限公司 | Electrochemical device, non-woven fabric ceramic diaphragm and preparation method thereof |
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Application publication date: 20141008 |