CN103354279A - Three-layer membrane for lithium ion battery - Google Patents
Three-layer membrane for lithium ion battery Download PDFInfo
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- CN103354279A CN103354279A CN2013102474845A CN201310247484A CN103354279A CN 103354279 A CN103354279 A CN 103354279A CN 2013102474845 A CN2013102474845 A CN 2013102474845A CN 201310247484 A CN201310247484 A CN 201310247484A CN 103354279 A CN103354279 A CN 103354279A
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The application discloses a three-layer membrane for a lithium ion battery. The membrane is composed of 3 composite layers, wherein a second composite layer is interlaid between a first composite layer and a third composite layer; the first composite layer comprises at least a heat-resistance layer with a porous structure; the second composite layer comprises at least a closed layer with a porous structure; the third composite layer comprises at least a ceramic layer with a porous structure. According to the membrane, the ceramic layer is in direct contact with the closed layer with a good surface coating property, thereby ensuring the peel strength and stability of the membrane. The heat-resistance layer can be used for guaranteeing the temperature resistance and mechanical strength of the membrane. Compared with a single-layer PP microporous membrane and a composite membrane with a ceramic coating, the three-layer membrane has the advantage that the high stability and the high tearing strength are guaranteed as the coating is unlikely to fall off. Compared with a single-layer PE microporous membrane and a composite membrane with a ceramic coating, the three-layer membrane has the advantage of better high temperature resistance.
Description
Technical field
The application relates to the battery diaphragm field, particularly relates to a kind of three layers of heatproof composite diaphragm for lithium ion battery.
Background technology
Microporous polypropylene membrane (PP film) and polyethene microporous membrane (PE film) are two kinds of stocks relatively commonly used in the battery diaphragm, and most composite diaphragm all is to be composited take PP microporous barrier or PE microporous barrier as basement membrane.At present, more common composite diaphragm has, take the PP microporous barrier as basement membrane, and coated ceramic coating on the PP microporous barrier; Perhaps take the PE microporous barrier as basement membrane, coated ceramic coating on the PE microporous barrier.The former closed pore temperature is high, has potential safety hazard, and PP microporous barrier surface is difficult for applying coating, and tearing strength is low between coating and basement membrane, easily comes off; Latter's heat resistance is poor, and under 120 ℃ or higher temperature, thermal contraction is very large, does not almost have mechanical strength, has equally potential safety hazard, and the composite diaphragm of PE microporous barrier basement membrane coated ceramic coating does not have real resistance to elevated temperatures.
Summary of the invention
The application's purpose provides a kind of heatproof composite diaphragm of three-decker of new construction.
For achieving the above object, the application has adopted following technical scheme:
The application discloses a kind of three layers of barrier film for lithium ion battery, comprises three composite beds, and the second composite bed is located between the first composite bed and the 3rd composite bed; The first composite bed is at least one deck heat-resistant layer of loose structure, and the second composite bed is that at least one deck of loose structure is closed layer, and the 3rd composite bed is at least one deck ceramic layer of loose structure.
Among the application, contain ceramic particle and the adhesive of mass ratio 0.1:1.0 to 1.0:0.1 in the ceramic layer.
Further, ceramic particle is selected from least a in the oxide particle of aluminium, silicon, magnesium and four kinds of metals of zirconium or the hydride particle; The average grain diameter of ceramic particle is 0.1-10 μ m.
Further, the melt temperature height of heat-resistant layer is closed at least 30 ℃ of the melt temperatures of layer.
Further, the peel strength between ceramic layer and the heat-resistant layer is greater than 2.0N/cm.
Among the application, heat-resistant layer and close layer and adopt hot pressing laminated or coextrusion is laminated.
Among the application, ceramic layer adopts coating method to be applied over described closing on the layer, and wherein coating method comprises any one in printing, the printing of nick version, compacting, roller coat, blade coating, dip-coating, spraying or the perfusion, preferred nick version printing and dip-coating.
Among the application, heat-resistant layer is one or more in polypropylene layer, polyvinylidene fluoride layer, Kynoar common hexafluoropropylene layer, PETG layer or the polyimide layer.
Among the application, close layer and be in the low density polyethylene layer, linear low density polyethylene layer, Tissuemat E layer one or more.
In the application's the optimal way, the concrete structure of three layers of barrier film comprises polypropylene layer, low density polyethylene layer and ceramic layer; Low density polyethylene layer is located between polypropylene layer and the ceramic layer.
Because adopt above technical scheme, the application's beneficial effect is:
Three layers of barrier film that are used for lithium ion battery of the application, ceramic layer directly contact with the surperficial closed pore layer that possesses fine coating characteristic, have guaranteed peel strength and the stability of barrier film, and the simultaneously existence of heat-resistant layer has also ensured heat resistance and the mechanical strength of barrier film.Three layers of barrier film of the application are compared with the composite diaphragm of ceramic coating with independent PP microporous barrier, and the coating difficult drop-off has ensured stability and the tearing strength of composite diaphragm; Compare with the composite diaphragm of ceramic coating with independent PE microporous barrier, have better resistance to elevated temperatures.
Description of drawings
Fig. 1: be the structural representation that is used for three layers of barrier film of lithium ion battery among the application's the embodiment.
Embodiment
Only there is in the market the PP microporous barrier to add ceramic coating or PE microporous barrier and adds two kinds of the ceramic coating composite diaphragms take PP microporous barrier or PE microporous barrier as basement membrane, these two kinds of composite diaphragms have exists inadequate, the caducous problem of tearing strength, and the temperature tolerance that has is inadequate.Three layers of barrier film that are used for lithium ion battery of the application are just for these shortcomings, improve on basis at existing composite diaphragm, propose the middle sandwiched of heat-resistant layer and ceramic layer and closed three basal layer structures of layer, not only improved tearing strength, solve caducous problem, and had preferably heat resistance.Need to prove that in three basal layers, each basal layer can be sandwich construction, in the first composite bed, can be that the heat-resistant layer of multilayer is composited, and then compound with the second composite bed.
Also by reference to the accompanying drawings the application is described in further detail below by concrete experimental example.Following experimental example only is further detailed the application, should not be construed as the restriction to the application.
Comparative Examples 1
This routine composite diaphragm is directly made at surface-coated one deck ceramic coating of microporous polypropylene membrane, concrete, the single face coating thickness is the ceramic coating of 5 μ m on the thick polypropylene micro-pore septum of 20 μ m, be prepared into the existing composite diaphragm that uses as a comparison, and test its ceramic coating adhesive force, 1 hour percent thermal shrinkage of 150 ℃ of heating, and hot closing temperature.Test result sees Table 1.
Comparative Examples 2
This routine composite diaphragm is directly made at surface-coated one deck ceramic coating of polyethene microporous membrane, concrete, the single face coating thickness is the ceramic coating of 5 μ m on the thick polyethylene micropore barrier film of 20 μ m, be prepared into existing be usefulness composite diaphragm as a comparison, and test its ceramic coating adhesive force, 1 hour percent thermal shrinkage of 150 ℃ of heating, and hot closing temperature.Test result sees Table 1.
Embodiment 1
The structure of three layers of barrier film that are used for lithium ion battery of this example comprises polypropylene diaphragm layer 1, ceramic coating 3 and is located in polypropylene diaphragm layer 1 and the polyethylene membrane layer 2 of ceramic coating 3 centres as shown in Figure 1.Concrete preparation method comprises, be that the polypropylene diaphragm of 10 μ m and polyethylene diaphragm hot-pressing that thickness is 10 μ m are laminated with thickness, then be the ceramic coating of 5 μ m at polyethylene barrier film face coating thickness, make the application's composite diaphragm, and test its ceramic coating adhesive force, 1 hour percent thermal shrinkage of 150 ℃ of heating, and hot closing temperature.Test result sees Table 1.
Embodiment 2
The structure of three layers of barrier film that are used for lithium ion battery of this example is identical with embodiment 1, just the preparation method changes to some extent, concrete, prepare the polypropylene, polyethylene compound substrate membranes that thickness is 22 μ m by coetrusion, apply the ceramic coating of 5 μ m behind the employing Celgard dry process stretching pore-forming at the polyethylene face, make the application's composite diaphragm, and test its ceramic coating adhesive force, 1 hour percent thermal shrinkage of 150 ℃ of heating, and hot closing temperature.Test result sees Table 1.
The performance test of table 1 composite diaphragm
According to the test result of table 1 as seen, compare with Comparative Examples 1, three layers of barrier film that are used for lithium ion battery of the application have overcome little, the caducous problem of polypropylene composite materials barrier film ceramic coating adhesive force of Comparative Examples 1; Compare with Comparative Examples 2, the percent thermal shrinkage of polyethylene composite diaphragm that three layers of barrier film that are used for lithium ion battery of the application have overcome Comparative Examples 2 is large, the shortcoming of non-refractory; Simultaneously, three layers of barrier film that are used for lithium ion battery of the application, also keep and continued Comparative Examples 1 and Comparative Examples 2 composite diaphragm a bit, when having good ceramic layer adhesive force, have less percent thermal shrinkage and lower hot closing temperature.
Above content is the further description of the application being done in conjunction with concrete execution mode, can not assert that the application's implementation is confined to these explanations.For the application person of an ordinary skill in the technical field, under the prerequisite that does not break away from the application's design, can also make some simple deduction or replace, all should be considered as belonging to the application's protection range.
Claims (10)
1. three layers of barrier film that are used for lithium ion battery, it is characterized in that: comprise three composite beds, the second composite bed is located between the first composite bed and the 3rd composite bed;
Described the first composite bed is at least one deck heat-resistant layer of loose structure, and described the second composite bed is that at least one deck of loose structure is closed layer, and described the 3rd composite bed is at least one deck ceramic layer of loose structure.
2. three layers of barrier film according to claim 1 is characterized in that: the ceramic particle and the adhesive that contain mass ratio 0.1:1.0 to 1.0:0.1 in the described ceramic layer.
3. three layers of barrier film according to claim 2 is characterized in that: described ceramic particle is selected from least a in the oxide particle of aluminium, silicon, magnesium and four kinds of metals of zirconium or the hydride particle; The average grain diameter of described ceramic particle is 0.1-10 μ m.
4. each described three layers of barrier films according to claim 1-3 is characterized in that: at least 30 ℃ of the high described melt temperatures of closing layer of the melt temperature of described heat-resistant layer.
5. each described three layers of barrier films according to claim 1-3, it is characterized in that: the peel strength between described ceramic layer and the described heat-resistant layer is greater than 2.0N/cm.
6. each described three layers of barrier films according to claim 1-3 is characterized in that: described heat-resistant layer and the described layer of closing adopt hot pressing laminated or coextrusion is laminated.
7. each described three layers of barrier films according to claim 1-3, it is characterized in that: described ceramic layer adopts coating method to be applied over described closing on the layer, described coating method comprises any one in printing, the printing of nick version, compacting, roller coat, blade coating, dip-coating, spraying or the perfusion, preferred nick version printing and dip-coating.
8. each described three layers of barrier films according to claim 1-3 is characterized in that: described heat-resistant layer is altogether one or more in hexafluoropropylene layer, PETG layer or the polyimide layer of polypropylene layer, polyvinylidene fluoride layer, Kynoar.
9. each described three layers of barrier films according to claim 1-3 is characterized in that: the described layer of closing is in low density polyethylene layer, linear low density polyethylene layer, the Tissuemat E layer one or more.
10. three layers of barrier film according to claim 9, it is characterized in that: the concrete structure of described three layers of barrier film comprises polypropylene layer, low density polyethylene layer and ceramic layer; Described low density polyethylene layer is located between polypropylene layer and the ceramic layer.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2013102474845A CN103354279A (en) | 2013-06-20 | 2013-06-20 | Three-layer membrane for lithium ion battery |
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| CN2013102474845A CN103354279A (en) | 2013-06-20 | 2013-06-20 | Three-layer membrane for lithium ion battery |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104157819A (en) * | 2014-09-02 | 2014-11-19 | 深圳市星源材质科技股份有限公司 | Ceramic-gel polymer multilayer composite lithium battery diaphragm and preparation method thereof |
| CN109192902A (en) * | 2018-07-10 | 2019-01-11 | 深圳中兴新材技术股份有限公司 | A kind of preparation method and lithium battery diaphragm of multilevel security protection lithium battery diaphragm |
| CN109860487A (en) * | 2019-01-18 | 2019-06-07 | 合肥国轩高科动力能源有限公司 | Lithium ion battery composite diaphragm and preparation method thereof |
| CN113224467A (en) * | 2021-05-27 | 2021-08-06 | 江苏星源新材料科技有限公司 | Coating diaphragm |
| CN113278310A (en) * | 2021-04-30 | 2021-08-20 | 惠州锂威新能源科技有限公司 | Composite ceramic particle and preparation method and application thereof |
| CN114566758A (en) * | 2021-12-29 | 2022-05-31 | 武汉中兴创新材料技术有限公司 | Film, preparation method thereof and battery comprising film |
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| CN1758463A (en) * | 2004-10-10 | 2006-04-12 | 西安迪纳斯科技有限责任公司 | Compound diaphragm used for lithium-ion secondary battery and lithium-ion secondary battery using the diaphragm |
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| WO2012070154A1 (en) * | 2010-11-26 | 2012-05-31 | トヨタ自動車株式会社 | Non-aqueous electrolyte secondary battery |
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| CN1679182A (en) * | 2002-08-24 | 2005-10-05 | 德古萨公司 | Electrical separator comprising a shut-down mechanism, method for the production thereof and its use in lithium batteries |
| CN1758463A (en) * | 2004-10-10 | 2006-04-12 | 西安迪纳斯科技有限责任公司 | Compound diaphragm used for lithium-ion secondary battery and lithium-ion secondary battery using the diaphragm |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104157819A (en) * | 2014-09-02 | 2014-11-19 | 深圳市星源材质科技股份有限公司 | Ceramic-gel polymer multilayer composite lithium battery diaphragm and preparation method thereof |
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| CN109192902A (en) * | 2018-07-10 | 2019-01-11 | 深圳中兴新材技术股份有限公司 | A kind of preparation method and lithium battery diaphragm of multilevel security protection lithium battery diaphragm |
| CN109860487A (en) * | 2019-01-18 | 2019-06-07 | 合肥国轩高科动力能源有限公司 | Lithium ion battery composite diaphragm and preparation method thereof |
| CN113278310A (en) * | 2021-04-30 | 2021-08-20 | 惠州锂威新能源科技有限公司 | Composite ceramic particle and preparation method and application thereof |
| CN113278310B (en) * | 2021-04-30 | 2022-06-17 | 惠州锂威新能源科技有限公司 | Composite ceramic particle and preparation method and application thereof |
| CN113224467A (en) * | 2021-05-27 | 2021-08-06 | 江苏星源新材料科技有限公司 | Coating diaphragm |
| CN114566758A (en) * | 2021-12-29 | 2022-05-31 | 武汉中兴创新材料技术有限公司 | Film, preparation method thereof and battery comprising film |
| CN114566758B (en) * | 2021-12-29 | 2024-03-29 | 武汉中兴创新材料技术有限公司 | Film, preparation method thereof and battery comprising film |
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Inventor after: Yu Changbu Inventor after: Cao Zhifeng Inventor before: Cao Zhifeng Inventor before: Ma Xiaoting |
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Free format text: CORRECT: INVENTOR; FROM: CAO ZHIFENG MA XIAOTING TO: YU CHANGPU CAO ZHIFENG |
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Application publication date: 20131016 |