CN203386832U - Three-layer membrane for lithium ion battery - Google Patents

Three-layer membrane for lithium ion battery Download PDF

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CN203386832U
CN203386832U CN201320356525.XU CN201320356525U CN203386832U CN 203386832 U CN203386832 U CN 203386832U CN 201320356525 U CN201320356525 U CN 201320356525U CN 203386832 U CN203386832 U CN 203386832U
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layer
layers
barrier film
membrane
ceramic
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曹志峰
麻小挺
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Shenzhen Zhongxing New Material Technology Co ltd
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SHENZHEN ZTE INNOVATION MATERIAL TECHNOLOGY Co Ltd
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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Abstract

The utility model relates to a three-layer membrane for a lithium ion battery. The three-layer membrane comprises three composite layers, wherein a second composite layer is clamped between a first composite layer and a third composite layer; the first composite layer refers to at least one temperature resistance layer with a porous structure; the second composite layer refers to at least one closing layer with a porous structure; the third composite layer refers to at least one ceramic layer with a porous structure. According to the membrane disclosed by the application of the utility model, the ceramic layer is in direct contact with a blind hole layer with a good surface coating property, the peel strength and the stability of the membrane are ensured; simultaneously, the temperature resistance performance and the mechanical strength of the membrane can be ensured due to the temperature resistance layer. Compared with a composite membrane of a single PP (polypropylene) microporous membrane and a ceramic coating, the membrane disclosed by the utility model has the advantages that a coating is unlikely to fall off, and thus the stability and the tearing strength of the membrane can be ensured; compared with a composite membrane of a single PE (polyethylene) microporous membrane and a ceramic coating, the membrane has the better high temperature resistance performance.

Description

Three layers of barrier film for lithium ion battery
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 battery diaphragm, and most composite diaphragm is all to take PP microporous barrier or PE microporous barrier to be composited as basement membrane.At present, more common composite diaphragm has, and take the PP microporous barrier as basement membrane, 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 between coating and basement membrane, tearing strength is low, easily comes off; Latter's heat resistance is poor, and at 120 ℃ or higher temperature, thermal contraction is very large, almost there is no 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 is to provide 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; At least one deck heat-resistant layer that the first composite bed is loose structure, at least one deck that the second composite bed is loose structure is closed layer, at least one deck ceramic layer that the 3rd composite bed is loose structure.
In the application, contain ceramic particle and the adhesive of mass ratio 0.1:1.0 to 1.0:0.1 in ceramic layer.
Further, ceramic particle is selected from aluminium, silicon, magnesium and the oxide particle of four kinds of metals of zirconium or at least one in hydride particle; The average grain diameter of ceramic particle is 0.1-10 μ m.
Further, high at least 30 ℃ of the melt temperatures of closing layer of the melt temperature of heat-resistant layer.
Further, the peel strength between ceramic layer and heat-resistant layer is greater than 2.0N/cm.
In the application, heat-resistant layer and close layer and adopt that hot pressing is laminated or coextrusion is laminated.
In the application, it is upper that ceramic layer adopts coating method to be applied over the described layer of closing, and wherein coating method comprises any one in printing, the printing of nick version, compacting, roller coat, blade coating, dip-coating, spraying or perfusion, preferably the printing of nick version and dip-coating.
In the application, heat-resistant layer is one or more in polypropylene layer, polyvinylidene fluoride layer, Kynoar common hexafluoropropylene layer, PETG layer or polyimide layer.
In the application, closing layer is one or more in low density polyethylene layer, linear low density polyethylene layer, Tissuemat E layer.
In the application's a 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 ceramic layer.
Owing to adopting above technical scheme, the application's beneficial effect is:
Three layers of barrier film for lithium ion battery of the application, ceramic layer directly contacts with the surperficial closed pore layer that possesses fine coating characteristic, has guaranteed peel strength and the stability of barrier film, and the existence of heat-resistant layer has simultaneously 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, there is better resistance to elevated temperatures.
The accompanying drawing explanation
Fig. 1: be for the structural representation of three layers of barrier film of lithium ion battery in the application's embodiment.
Embodiment
Only having in the market the PP microporous barrier to add ceramic coating or PE microporous barrier adds two kinds of ceramic coating and take the composite diaphragm that PP microporous barrier or PE microporous barrier be basement membrane, these two kinds of composite diaphragms have exists inadequate, the caducous problem of tearing strength, and some temperature tolerances are inadequate.Three layers of barrier film for lithium ion battery of the application are just for these shortcomings, on the basis of existing composite diaphragm, improved, 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 there is heat resistance preferably.It should be noted 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.
Below by concrete experimental example, also by reference to the accompanying drawings the application is described in further detail.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 ceramic coating that on thick polypropylene micro-pore septum, the single face coating thickness is 5 μ m at 20 μ m, be prepared into the existing composite diaphragm used as a comparison, and test its ceramic coating adhesive force, 150 ℃ of heating percent thermal shrinkage of 1 hour, and hot closing temperature.Test result is in 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 ceramic coating that on thick polyethylene micropore barrier film, the single face coating thickness is 5 μ m at 20 μ m, be prepared into existing be use composite diaphragm as a comparison, and test its ceramic coating adhesive force, 150 ℃ of heating percent thermal shrinkage of 1 hour, and hot closing temperature.Test result is in Table 1.
Embodiment 1
The structure of three layers of barrier film for lithium ion battery of this example as shown in Figure 1, 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.Concrete preparation method comprises, the polyethylene diaphragm hot-pressing that the polypropylene diaphragm that is 10 μ m by thickness and thickness are 10 μ m is laminated, then the ceramic coating that is 5 μ m at polyethylene barrier film face coating thickness, make the application's composite diaphragm, and test its ceramic coating adhesive force, 150 ℃ of heating percent thermal shrinkage of 1 hour, and hot closing temperature.Test result is in Table 1.
Embodiment 2
The structure of three layers of barrier film for lithium ion battery of this example is identical with embodiment 1, just the preparation method changes to some extent, concrete, prepare by coetrusion the polypropylene, polyethylene compound substrate membranes that thickness is 22 μ m, apply the ceramic coating of 5 μ m after employing Celgard dry process stretching pore-forming at the polyethylene face, make the application's composite diaphragm, and test its ceramic coating adhesive force, 150 ℃ of heating percent thermal shrinkage of 1 hour, and hot closing temperature.Test result is in Table 1.
The performance test of table 1 composite diaphragm
Figure BDA00003379065200031
Visible according to the test result of table 1, with Comparative Examples 1, to compare, three layers of barrier film 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; With Comparative Examples 2, compare, the percent thermal shrinkage of polyethylene composite diaphragm that three layers of barrier film 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 for lithium ion battery of the application, also retain and the composite diaphragm that continued Comparative Examples 1 and Comparative Examples 2 a little, when thering is good ceramic layer adhesive force, there is 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 concrete enforcement 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 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;
At least one deck heat-resistant layer that described the first composite bed is loose structure, at least one deck that described the second composite bed is loose structure is closed layer, at least one deck ceramic layer that described the 3rd composite bed is loose structure.
2. three layers of barrier film according to claim 1, it is characterized in that: the ceramic particle of described ceramic layer is selected from aluminium, silicon, magnesium and the oxide particle of four kinds of metals of zirconium or at least one in hydride particle; The average grain diameter of described ceramic particle is 0.1-10 μ m.
3. three layers of barrier film according to claim 1 and 2 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.
4. three layers of barrier film according to claim 1 and 2, it is characterized in that: the peel strength between described ceramic layer and described heat-resistant layer is greater than 2.0N/cm.
5. three layers of barrier film according to claim 1 and 2 is characterized in that: described heat-resistant layer and the described layer of closing adopt that hot pressing is laminated or coextrusion is laminated.
6. three layers of barrier film according to claim 1 and 2, it is characterized in that: it is upper that described ceramic layer adopts coating method to be applied over the described layer of closing, and described coating method comprises any one in printing, the printing of nick version, compacting, roller coat, blade coating, dip-coating, spraying or perfusion.
7. three layers of barrier film according to claim 6, it is characterized in that: described coating method is the printing of nick version or dip-coating.
8. three layers of barrier film according to claim 1 and 2 is characterized in that: described heat-resistant layer is polypropylene layer, polyvinylidene fluoride layer, Kynoar one or more in hexafluoropropylene layer, PETG layer or polyimide layer altogether.
9. three layers of barrier film according to claim 1 and 2 is characterized in that: the described layer of closing is for one or more in low density polyethylene layer, linear low density polyethylene layer, Tissuemat E layer.
10. three layers of barrier film according to claim 9, it is characterized in that: described three layers of barrier film specifically comprise polypropylene layer, low density polyethylene layer and ceramic layer; Described low density polyethylene layer is located between polypropylene layer and ceramic layer.
CN201320356525.XU 2013-06-20 2013-06-20 Three-layer membrane for lithium ion battery Expired - Lifetime CN203386832U (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104022250A (en) * 2014-06-26 2014-09-03 佛山市盈博莱科技有限公司 Lithium ion battery diaphragm and preparation method
CN109301136A (en) * 2018-11-28 2019-02-01 河北金力新能源科技股份有限公司 A kind of heat-resisting lithium battery diaphragm and preparation method thereof
CN110649213A (en) * 2019-09-05 2020-01-03 西安科技大学 Coating diaphragm material for lithium-sulfur secondary battery and application thereof
CN111192996A (en) * 2019-12-17 2020-05-22 山东海科创新研究院有限公司 Organic coating/polyethylene composite diaphragm, preparation method thereof and lithium ion battery

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104022250A (en) * 2014-06-26 2014-09-03 佛山市盈博莱科技有限公司 Lithium ion battery diaphragm and preparation method
CN104022250B (en) * 2014-06-26 2016-08-24 佛山市盈博莱科技股份有限公司 A kind of lithium ion battery separator and preparation method thereof
CN109301136A (en) * 2018-11-28 2019-02-01 河北金力新能源科技股份有限公司 A kind of heat-resisting lithium battery diaphragm and preparation method thereof
CN110649213A (en) * 2019-09-05 2020-01-03 西安科技大学 Coating diaphragm material for lithium-sulfur secondary battery and application thereof
CN110649213B (en) * 2019-09-05 2022-09-16 西安科技大学 Coating diaphragm material for lithium-sulfur secondary battery and application thereof
CN111192996A (en) * 2019-12-17 2020-05-22 山东海科创新研究院有限公司 Organic coating/polyethylene composite diaphragm, preparation method thereof and lithium ion battery

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Address after: 518120 No. 8 Binhai Road, Dapeng street, Dapeng New District, Shenzhen, Guangdong, China.

Patentee after: SHENZHEN ZHONGXING NEW MATERIAL TECHNOLOGY Co.,Ltd.

Address before: 518000 block D, office building, Hanhan Innovation Park, Langshan Road, Nanshan District, Shenzhen, Guangdong 503

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