CN104091908A - Polymer diaphragm with hard plastic/ceramic composite structure - Google Patents
Polymer diaphragm with hard plastic/ceramic composite structure Download PDFInfo
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- CN104091908A CN104091908A CN201410287936.7A CN201410287936A CN104091908A CN 104091908 A CN104091908 A CN 104091908A CN 201410287936 A CN201410287936 A CN 201410287936A CN 104091908 A CN104091908 A CN 104091908A
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- Prior art keywords
- polymer
- membrane
- hard plastic
- ceramic composite
- polymeric matrix
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a polymer diaphragm with a hard plastic/ceramic composite structure. The polymer diaphragm is characterized by comprising an inner microporous membrane and an outer membrane and is formed by coating the surface of the inner microporous membrane with a filler-containing polymeric matrix, wherein a solution is prepared by dissolving the polymeric matrix into a solvent, fillers which are insoluble in the solvent are added and uniformly dispersed, the both surfaces of the inner microporous membrane are coated with the solution to form membranes; the outer membrane is formed by coating the inner microporous membrane with the polymeric matrix and the fillers, the solution with the certain concentration is prepared by dissolving the polymeric matrix into the solvent, polymer granules which are insoluble in the solvent or mixtures of the polymer granules and inorganic particles are added, the fillers are uniformly dispersed in the polymeric matrix solution by ultrasonication, mechanical stirring and the like, the both surfaces of the inner microporous membrane are coated with the polymeric matrix solution to form the membranes, and further thermocompression bonding is carried out.
Description
Technical field
The present invention relates to a kind of membrane for polymer that contains hard plastic/ceramic composite structures, 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 security 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 break-through and the scale application of electrokinetic 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 critical component of barrier film lithium battery, the security performance of battery is played an important role.
Barrier film between both positive and negative polarity has electrolyte ion transmission channel, prevents the effect of both positive and negative polarity contact short circuit.Yet current used TPO barrier film melting closed porosity when battery temperature is too high, intercepts the transmission of electrolyte ion, reduces security risk; But because the heat resistance of polyolefin 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 performance and heat resistance, for example membrane surface coating inorganic particle or polymer and inorganic particulate are made composite 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 polymer of mechanical performance 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 polymeric material of barrier film itself, can there is the reaction (for example publication number US2012/0295154 A1) of similar closed pore effect, or add other polymer that can realize closed pore effect etc. (for example publication number CN 101656306A, publication number US2013/0022858 A1).
Summary of the invention
The object of the present invention is to provide a kind of membrane for polymer that contains hard plastic/ceramic composite structures; its outer membrane is applied and forms at internal layer microporous barrier by polymeric matrix and filler; polymeric matrix is dissolved in solvent and makes certain density solution; add and be insoluble to the polymer beads of this solvent or the mixture of polymer beads and inorganic particulate; utilize ultrasonic, mechanical agitation etc. that uniform filling is dispersed in Polymers liquid solution; be coated in internal layer microporous barrier two sides film forming, further hot binding.
Technical scheme of the present invention is achieved in that a kind of membrane for polymer that contains hard plastic/ceramic composite structures, it is characterized in that: comprise internal layer microporous barrier and outer membrane, by forming in internal layer microporous barrier surface-coated containing Packed polymeric matrix, wherein polymeric matrix is dissolved in solvent and makes solution, add that to be insoluble to the fillers dispersed of this solvent even, be coated in internal layer microporous barrier two sides film forming.
Described filler is polymer beads or polymer beads/inorganic particulate mixture.
Described melting of polymer pellets temperature >=180 ℃.
Described polymer beads is a kind of in polyether-ketone, polyether-ether-ketone, polyether ether ketone ketone, polyetherketoneetherketoneketone, polybenzothiozole, polybenzimidazoles, polyphenylene sulfide or their combination.
Described inorganic particulate is a kind of in silicon dioxide, titanium dioxide, calcium oxide, barium titanate or their combination.
Described outer membrane is that polymeric matrix is dissolved in solvent and makes solution, adds that to be insoluble to the fillers dispersed of this solvent even, is coated in internal layer microporous barrier two sides film forming.
Good effect of the present invention is that outer membrane is applied and forms at internal layer microporous barrier by polymeric matrix and filler, and the polymer beads of interpolation has improved the mechanical performance 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, polymer beads, in molten condition, can further stop the transmission of electrolyte ion, reduces the chemical reaction of battery, the fail safe that improves battery.
Accompanying drawing explanation
Fig. 1 barrier film schematic diagram of the present invention.
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 drawings and Examples, the present invention will be further described: as shown in Figure 1; polymeric matrix is dissolved in acetone; NMP; a kind of or combination solvent in DMF; the solution of polymeric matrix/solvent quality ratio=0.13～0.17 is made in acetone/NMP/DMF=0～1/0～1/0～1; add and be insoluble to the polymer beads of this solvent or the mixture of polymer beads and inorganic particulate; utilize ultrasonic, mechanical agitation etc. that uniform filling is dispersed in Polymers liquid solution; be coated in internal layer microporous barrier two sides film forming, further hot binding.In the present invention, the polymeric matrix that uses can be a kind of in Kynoar, Kynoar-hexafluoropropylene or their combination; Microporous barrier used can be a kind of of polyethylene, polypropylene and polyethylene/polypropylene composite membrane or their combination; Filler used is the above polymer beads of 180 ℃ of melt temperatures, can be polyether-ketone, polyether-ether-ketone, polyether ether ketone ketone, a kind of in polyetherketoneetherketoneketone, polybenzothiozole, polybenzimidazoles, polyphenylene sulfide or their combination; Described inorganic particulate can be silicon dioxide, titanium dioxide, calcium oxide, graphene oxide, barium titanate.
Embodiment 1
(1) 7.5g Kynoar-hexafluoropropylene is dissolved in 48g acetone, through heating, strong stirring, after fully dissolving, it adds ultra-fine polyether ether ketone ketone 2.25g, continue heating, stir after a period of time, add 0.5g silicon dioxide, continue to stir, obtain dispersed colloid mixed liquor preferably; (2) in the colloid mixed liquor in step (1), dropwise add the absolute ethyl alcohol of 6.0g as pore-foaming agent, continue to stir; (3) the colloid mixed liquor 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.The carrying out of preparing with this embodiment thermal contraction and tension test, experimental data is shown in Fig. 2 and table 1.From data, the good heat resistance of this barrier film, at 165 ℃ almost without shrinking; Stretch and contrast with certain commercialization barrier film, this barrier film shows good mechanical performance.
Embodiment 2
(1) 7.5g Kynoar is dissolved in 46g acetone, through heating, strong stirring, after it fully dissolves; (2) to (1), add ultra-fine polyether-ether-ketone 0.45g, continue heating, stir after a period of time, obtain dispersed colloid mixed liquor preferably; (3) in (2), add calcium oxide 0.15g to continue heating, stir; (4) the colloid mixed liquor of step (3) 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 Kynoar-hexafluoropropylene is dissolved in 46g acetone, through heating, strong stirring, after it fully dissolves, adds the mixture 1.35g of ultra-fine polyether-ketone and polybenzimidazoles, continue heating, stir; (2) to (1), add 0.45g barium titanate, stir after a period of time, obtain dispersed colloid mixed liquor preferably; (3) in the colloid mixed liquor in step (2), dropwise add the n-butanol of 5.0g as pore-foaming agent, continue to stir; (4) the colloid mixed liquor of step (3) is coated in to the two sides of micro-pore septum; (5) 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 Kynoar is dissolved in 48g NMP, through heating, strong stirring, after it fully dissolves, adds the mixture 0.45g of ultra-fine polyphenylene sulfide and ultra-fine polybenzimidazoles, continue heating, stir; (2) to step (1), add 0.30g titanium dioxide, stir after a period of time, obtain dispersed colloid mixed liquor preferably; (3) in the colloid mixed liquor in step (2), dropwise add the n-butanol of 5.0g as pore-foaming agent, continue to stir; (4) micro-pore septum is by 2h in the colloid mixed liquor of impregnation steps (3); (5). 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 Kynoar is dissolved in 23g NMP and 23g acetone, through heating, strong stirring, after it fully dissolves, adds the mixture 1.125g of ultra-fine polyetherketoneetherketoneketone and ultra-fine polybenzothiozole, continue heating, stir; (2) in step (1), add 0.375g silicon dioxide, 0.125g barium titanate, stirred after a period of time, obtained dispersed colloid mixed liquor preferably; (3) in the colloid mixed liquor in step (2), dropwise add the n-butanol of 4.5g as pore-foaming agent, continue to stir; (4) the colloid mixed liquor of step (3) is coated in to the two sides of micro-pore septum; (5) take off film by after its roll-in, at the temperature of 70 ℃, film is carried out to 2h vacuum drying.
Claims (5)
1. a membrane for polymer that contains hard plastic/ceramic composite structures, it is characterized in that: comprise internal layer microporous barrier and outer membrane, by forming in internal layer microporous barrier surface-coated containing Packed polymeric matrix, wherein polymeric matrix is dissolved in solvent and makes solution, add that to be insoluble to the fillers dispersed of this solvent even, be coated in internal layer microporous barrier two sides film forming.
2. a kind of membrane for polymer that contains hard plastic/ceramic composite structures according to claim 1, is characterized in that described filler is polymer beads or polymer beads/inorganic particulate mixture.
3. a kind of membrane for polymer that contains hard plastic/ceramic composite structures according to claim 2, is characterized in that described melting of polymer pellets temperature >=180 ℃.
4. according to claim 2, a kind of membrane for polymer that contains hard plastic/ceramic composite structures described in 3, is characterized in that described polymer beads is a kind of in polyether-ketone, polyether-ether-ketone, polyether ether ketone ketone, polyetherketoneetherketoneketone, polybenzothiozole, polybenzimidazoles, polyphenylene sulfide or their combination.
5. a kind of membrane for polymer that contains hard plastic/ceramic composite structures 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410287936.7A CN104091908A (en) | 2014-06-25 | 2014-06-25 | Polymer diaphragm with hard plastic/ceramic composite structure |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410287936.7A CN104091908A (en) | 2014-06-25 | 2014-06-25 | Polymer diaphragm with hard plastic/ceramic composite structure |
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| CN104091908A true CN104091908A (en) | 2014-10-08 |
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| CN201410287936.7A Pending CN104091908A (en) | 2014-06-25 | 2014-06-25 | Polymer diaphragm with hard plastic/ceramic composite structure |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114497899A (en) * | 2022-02-11 | 2022-05-13 | 北京宇程科技有限公司 | High-temperature-resistant polymer microsphere coated modified composite diaphragm and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103618059A (en) * | 2013-12-10 | 2014-03-05 | 深圳市星源材质科技有限公司 | Lithium ion battery diaphragm with polymer inorganic coating and preparation method for lithium ion battery diaphragm |
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2014
- 2014-06-25 CN CN201410287936.7A patent/CN104091908A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103618059A (en) * | 2013-12-10 | 2014-03-05 | 深圳市星源材质科技有限公司 | Lithium ion battery diaphragm with polymer inorganic coating and preparation method for lithium ion battery diaphragm |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114497899A (en) * | 2022-02-11 | 2022-05-13 | 北京宇程科技有限公司 | High-temperature-resistant polymer microsphere coated modified composite diaphragm and preparation method thereof |
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Application publication date: 20141008 |