CN203134887U - Ceramic composite diaphragm having high liquid absorbing rate and high heat resistance - Google Patents
Ceramic composite diaphragm having high liquid absorbing rate and high heat resistance Download PDFInfo
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- CN203134887U CN203134887U CN2012206994229U CN201220699422U CN203134887U CN 203134887 U CN203134887 U CN 203134887U CN 2012206994229 U CN2012206994229 U CN 2012206994229U CN 201220699422 U CN201220699422 U CN 201220699422U CN 203134887 U CN203134887 U CN 203134887U
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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
Abstract
The utility model relates to a ceramic composite diaphragm having high liquid absorbing rate and high heat resistance. The ceramic composite diaphragm is characterized in that a flexible macromolecule polymer is used as a substrate, an inorganic ceramic diaphragm covers the surface of the substrate, the thickness of the macromolecule substrate is 10 to 50 micrometers, the thickness of a ceramic coating is 2 to 10 micrometers, the ceramic coating is coated on a single side or two sides, the diaphragm consists of three layers or five layers, the three layers correspond to the single-side coating, one layer is the macromolecule polymer substrate layer, another layer is a transitional layer containing a coupler, and a third layer is a ceramic layer; and the five layers correspond to the two-side coating, two sides of the macromolecule polymer substrate are respectively coated with a coupler layer, and the surfaces of the two coupler layers are respectively the inorganic ceramic layers. The ionic conductivity of an electrolyte of a lithium ion battery adopting the ceramic composite diaphragm as a diaphragm is high, the overall cycling performance of the battery and the safety of the battery can be greatly improved; and the ceramic composite diaphragm can be used for a liquid lithium ion battery and also can be used for a polymer lithium ion battery or a gel-type polymer battery.
Description
Technical field
The utility model relates to a kind of Ceramic Composite barrier film with high-liquid absorbing rate and heat resistance, is a kind of polymer/inorganic thing Ceramic Composite barrier film, can be applied to once reach the secondary power supply field.
Background technology
The barrier film of lithium ion battery is positioned between the battery plus-negative plate as one of critical piece of battery, has the effect of insulation electronics, transmission lithium ion.As having high value-added product, battery diaphragm especially lithium battery diaphragm is mainly grasped by states such as U.S., Japan and Korea S., and the new types of diaphragm that exploitation has independent intellectual property right extremely is necessary.
Commercial separator product is generally PE, PP, PP/PE/PP.These supra polymer linear polyethylenes, polypropylene material, because the intrinsic physical characteristic of material, the PE material is about 135 ℃, and the PP material is about 165 ℃, and barrier film is realized closed pore, and at this moment, battery is in off state.When internal temperature of battery further raises, the barrier film fusion, the battery plus-negative plate contact, short circuit causes violent exothermic reaction, the problem of very easily blasting.
Barrier film research based on hot safety problem, high-liquid absorbing rate, high room temperature and low-temperature ion conductivity is the focus of current research and development.Number of patent application US2008028381A1 adopts KH-792, KH550, and coupling agents such as KH570 are with inorganic particulate such as ZrO
2, SiO
2, Al
2O
3(1-99%) and zeolite (1-25%) be coupled at barrier film, resulting barrier film has thermodynamic property and room temperature/low-temperature ion conductivity preferably.Yet, owing to do not contain polar group in the strand of barrier film commonly used, surface inertness, the interaction strength of above-mentioned coupling agent and barrier film matrix is very not strong, thereby cause inorganic ceramic material the coming off in the long-term use of lithium ion battery of membrane surface, influence the useful life of lithium ion battery.
Number of patent application CN101481855A discloses a kind of silicon dioxide/Kynoar composite diaphragm, its preparation method is more simple, after being about to raw material silicon dioxide and polyvinylidene blending, prepare diaphragm material by electrospinning process, obviously, the composite diaphragm that the method obtains exists problem of phase separation, can not satisfy the long-term instructions for use of lithium ion battery.
Summary of the invention
The purpose of this utility model is to provide a kind of Ceramic Composite barrier film with high-liquid absorbing rate and heat resistance, it is with polymer-based surface weak oxide, obtain the matrix that the surface carries the surface modification of hydroxyl, adopt two kinds to have interactional coupling agent and handle matrix and inorganic particulate respectively then, interaction by two kinds of coupling agents, strengthened the interaction of inorganic nano-particle and organic matrix, it has stronger stability, stronger imbibition/liquid-keeping property and thermal shock resistance, be the ionic conductivity of the lithium ion battery of barrier film with it, cycle performance and security performance have had raising by a relatively large margin; Its preparation method is easy and simple to handle, and environmental requirement is low, pollutes little.
To achieve these goals, the technical solution of the utility model is achieved in that a kind of Ceramic Composite barrier film with high-liquid absorbing rate and heat resistance, it is characterized in that: the high molecular polymer with flexibility is matrix, cover the inorganic ceramic barrier film at matrix surface, the matrix thickness of high molecular polymer is 10 ~ 50 μ m, the thickness of ceramic coating is 2 ~ 10 μ m, ceramic coating is single face or dual coating, and wherein high molecular polymer is polyethylene (PE), polypropylene (PE), polyethylene glycol oxide (PEO), polymethyl methacrylate (PMMA), Kynoar (PVDF), polyacrylonitrile (PAN) or based on one or more of the synthetic polymer of certain material wherein; Inorganic ceramic material is SiO
2, Al
2O
3, TiO
2, ZrO
2Perhaps MgO, also can be in above-mentioned material additional proportion be no more than the 40%(mass fraction) zeolite, the diameter of inorganic ceramic and zeolite granular has higher dispersiveness less than 2 microns in solution.
Described Ceramic Composite barrier film is formed by three layers or five layers, three layers of correspondence be that single face applies, one deck is the high molecular polymer matrix, another layer is the transition zone of coupling agent composition, the 3rd layer is ceramic layer; Five layers of correspondence be dual coating, the matrix double-faced coated with coupling agent layer of high molecular polymer, two-sided coupling agent layer surface is inorganic, ceramic layer.
Good effect of the present utility model is that inorganic particulate is linked together with macromolecule matrix closely, thereby strengthened the stability of macromolecule/inorganic compounding barrier film, it has stronger stability, stronger imbibition/liquid-keeping property and thermal shock resistance, be the electrolytical ionic conductivity of the lithium ion battery of barrier film with it, cell integrated cycle performance and security performance have had raising by a relatively large margin; Liquid lithium ion battery can be used for, polymer Li-ion battery or gel-type polymer battery can be used for simultaneously.
Description of drawings
Fig. 1 is structural representation of the present utility model.The 1st, PVDF layer, the 3rd, MgO layer, 2 is coupling agent layer at the interface.
Embodiment
Below in conjunction with drawings and Examples the utility model is further described: as shown in Figure 1A kind of Ceramic Composite barrier film with high-liquid absorbing rate and heat resistance, it is characterized in that: the high molecular polymer with flexibility is matrix, cover the inorganic ceramic barrier film at matrix surface, the matrix thickness of high molecular polymer is 10 ~ 50 μ m, the thickness of ceramic coating is 2 ~ 10 μ m, ceramic coating is single face or dual coating, and wherein high molecular polymer is polyethylene (PE), polypropylene (PE), polyethylene glycol oxide (PEO), polymethyl methacrylate (PMMA), Kynoar (PVDF), polyacrylonitrile (PAN) or based on one or more of the synthetic polymer of certain material wherein; Inorganic ceramic material is SiO
2, Al
2O
3, TiO
2, ZrO
2Perhaps MgO, also can be in above-mentioned material additional proportion be no more than the 40%(mass fraction) zeolite, the diameter of inorganic ceramic and zeolite granular has higher dispersiveness less than 2 microns in solution.
Described Ceramic Composite barrier film is formed by three layers or five layers, three layers of correspondence be that single face applies, one deck is the high molecular polymer matrix, another layer is the transition zone of coupling agent composition, the 3rd layer is ceramic layer; Five layers of correspondence be dual coating, the matrix double-faced coated with coupling agent layer of high molecular polymer, two-sided coupling agent layer surface is inorganic, ceramic layer.
High molecular polymer polyethylene (PE) microporous barrier with flexibility is matrix, the composite diaphragm of two-sided covering inorganic, ceramic layer, and wherein the polyethylene micropore film thickness is 12 μ m, and the thickness of ceramic layer is 2 μ m, and inorganic ceramic material is SiO
2,The diameter of inorganic ceramic particle is 550nm.
High molecular polymer polypropylene (PP) microporous barrier with flexibility is matrix, and single face covers the composite diaphragm of inorganic, ceramic layer, and wherein PP microporous barrier thickness is 16 μ m, and the thickness of ceramic layer is 3 μ m, and inorganic ceramic material is Al
2O
3,The diameter of inorganic ceramic particle is 400nm.
Embodiment 3
High molecular polymer Kynoar (PVDF) non-weaving cloth with flexibility is matrix, the composite diaphragm of two-sided covering inorganic, ceramic layer, and wherein the thickness of PVDF non-weaving cloth is 36 μ m, and the thickness of ceramic layer is 2 μ m, and inorganic ceramic material is MgO
,The diameter of inorganic ceramic particle is 440nm.
Embodiment 4
High molecular polymer PETG (terylene with flexibility, PET) non-weaving cloth is matrix, the composite diaphragm of two-sided covering inorganic, ceramic layer, wherein the thickness of PET non-weaving cloth is 40 μ m, the thickness of ceramic layer is 3 μ m, inorganic ceramic material is ZrO/ zeolite (mass ratio is 80/20), and the diameter of inorganic ceramic particle is 600nm.
Claims (2)
1. Ceramic Composite barrier film with high-liquid absorbing rate and heat resistance, high molecular polymer and inorganic ceramic barrier film by flexibility are formed, it is characterized in that: the high molecular polymer with flexibility is matrix, cover the inorganic ceramic barrier film at matrix surface, the matrix thickness of high molecular polymer is 10 ~ 50 μ m, the thickness of ceramic coating is 2 ~ 10 μ m, and ceramic coating is single face or dual coating.
2. a kind of Ceramic Composite barrier film with high-liquid absorbing rate and heat resistance according to claim 1, it is characterized in that described Ceramic Composite barrier film forms by three layers or five layers, three layers of correspondence be that single face applies, one deck is the high molecular polymer matrix, the transition zone that another layer formed for coupling agent, the 3rd layer is ceramic layer; Five layers of correspondence be dual coating, the matrix double-faced coated with coupling agent layer of high molecular polymer, two-sided coupling agent layer surface is inorganic, ceramic layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012206994229U CN203134887U (en) | 2012-12-18 | 2012-12-18 | Ceramic composite diaphragm having high liquid absorbing rate and high heat resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012206994229U CN203134887U (en) | 2012-12-18 | 2012-12-18 | Ceramic composite diaphragm having high liquid absorbing rate and high heat resistance |
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| Publication Number | Publication Date |
|---|---|
| CN203134887U true CN203134887U (en) | 2013-08-14 |
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ID=48942832
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012206994229U Expired - Fee Related CN203134887U (en) | 2012-12-18 | 2012-12-18 | Ceramic composite diaphragm having high liquid absorbing rate and high heat resistance |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104600229A (en) * | 2015-01-28 | 2015-05-06 | 湖北科技学院 | Preparation method of ceramic grafted diaphragm and application of ceramic grafted diaphragm in lithium battery |
| CN104746236A (en) * | 2013-12-25 | 2015-07-01 | 比亚迪股份有限公司 | Polyimide/polyethylene oxide cable type composite nanometer fiber membrane and preparation method thereof |
| CN110289381A (en) * | 2019-05-09 | 2019-09-27 | 湖南文理学院 | A kind of diaphragm for lithium ion battery and preparation method |
-
2012
- 2012-12-18 CN CN2012206994229U patent/CN203134887U/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104746236A (en) * | 2013-12-25 | 2015-07-01 | 比亚迪股份有限公司 | Polyimide/polyethylene oxide cable type composite nanometer fiber membrane and preparation method thereof |
| CN104600229A (en) * | 2015-01-28 | 2015-05-06 | 湖北科技学院 | Preparation method of ceramic grafted diaphragm and application of ceramic grafted diaphragm in lithium battery |
| CN104600229B (en) * | 2015-01-28 | 2017-03-15 | 湖北科技学院 | A kind of pottery grafting barrier film preparation method and its application in lithium battery |
| CN110289381A (en) * | 2019-05-09 | 2019-09-27 | 湖南文理学院 | A kind of diaphragm for lithium ion battery and preparation method |
| CN110289381B (en) * | 2019-05-09 | 2021-09-28 | 湖南文理学院 | Diaphragm for lithium ion battery and preparation method |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130814 Termination date: 20191218 |