CN103811699A - Isolation film for lithium ion secondary battery, and making method thereof - Google Patents
Isolation film for lithium ion secondary battery, and making method thereof Download PDFInfo
- Publication number
- CN103811699A CN103811699A CN201210444056.7A CN201210444056A CN103811699A CN 103811699 A CN103811699 A CN 103811699A CN 201210444056 A CN201210444056 A CN 201210444056A CN 103811699 A CN103811699 A CN 103811699A
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- Prior art keywords
- barrier film
- lithium
- acrylonitrile copolymer
- rechargeable battery
- isolation film
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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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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
-
- 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
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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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses an isolation film for a lithium ion secondary battery. The isolation film comprises a polyolefin isolation film substrate, and one or two of the two sides of the polyolefin isolation film substrate is/are coated with a nanocoating formed by one or two of zirconia, alumina, silicon oxide, silicon nitride and aluminum nitride. The nanocoating and the polyolefin isolation film substrate are bonded through a lithium acrylate-acrylonitrile copolymer. The aqueous dispersion of the lithium acrylate-acrylonitrile copolymer is adopted, and deionized water is also adopted as a solvent, so the production process of the isolation film is simple, toxic gases polluting the environment are not emitted, and fire risks can be avoided; and the lithium acrylate-acrylonitrile copolymer has a very high electrochemical stability, and cannot be oxidized or decomposed even if the voltage reaches 4.5V, so batteries made by using the isolation film have long term reliability and safety.
Description
Technical field
The invention belongs to chemical field, relate to a kind of lithium rechargeable battery barrier film and preparation method thereof.
Background technology
Prior art, prepare lithium rechargeable battery barrier film and mainly contain three kinds of patterns:
The first pattern: copolymer from vinylidene fluoride and hexafluoropropylene is dissolved in to the Organic solvents such as acrylic carbonic ester, ethyl acetate, butyl acetate, carbonic acid ethyl methyl esters, acetone, add one or both in a certain proportion of nano level zirconia, aluminium oxide, silica, silicon nitride, aluminium nitride, mode by spraying, immersion or directly coating is attached to metal oxide or nitride in one side or two sides of polyolefine isolating film base material, coating thickness is generally 1-5um, obtains the lithium rechargeable battery barrier film after modification.
The second pattern: add a certain proportion of deionized water in SBR emulsion, after stirring, add one or both in a certain proportion of nano level zirconia, aluminium oxide, silica, silicon nitride, aluminium nitride, mode by spraying, immersion or directly coating is attached to metal oxide or nitride in one side or two sides of polyolefine isolating film base material, coating thickness is generally 1-5um, obtains the lithium rechargeable battery barrier film after modification.
Shortcoming by prior art:
What the first pattern had employing is organic solvent, and what adopt is than the solvent that is easier to volatilization, the possibility that has disaster hidden-trouble and atmosphere pollution in the process using, these organic solvents of Long Term Contact also can produce harm to human body, therefore its operation are had relatively high expectations
What the second pattern adopted is that SBR emulsion is as binding agent, nano-metal-oxide or nitride are adhered on polyolefinic barrier film base material, for lithium battery, because the current potential of lithium battery anode is higher, close anodal barrier film is on one side also under high potential, and butadiene-styrene rubber is worked for a long time and easily occurred to be oxidized and to decompose under high potential, causes losing the function of bonding, originally adhere to get on metal oxide or nitride and come off, lose original function.
Summary of the invention
Technical problem to be solved by this invention is not adopt organic solvent with respect to the first pattern, does not have the problem to harm and environmental pollution, and does not worry disaster hidden-trouble; With respect to the second pattern, this programme possesses long term reliability.
It is as follows that the present invention solves the problems of the technologies described above taked technical scheme:
A kind of lithium rechargeable battery barrier film, comprise the base material of polyolefine isolating film, the one or both sides of the base material of described polyolefine isolating film are coated with one or both nano coatings that form in zirconia, aluminium oxide, silica, silicon nitride, aluminium nitride.
The base material of described nano coating and described polyolefine isolating film is bonded together by Lithium acrylate and acrylonitrile copolymer.
A preparation method for barrier film for lithium rechargeable battery, comprising:
(1) aqueous dispersions of Lithium acrylate and acrylonitrile copolymer is added in deionized water;
(2) one or both in interpolation nanoscale zirconia, aluminium oxide, silica, silicon nitride, aluminium nitride, stir and grind;
(3) one or both of described nanoscale zirconia after treatment step (2), aluminium oxide, silica, silicon nitride, aluminium nitride are attached in a side or two sides of polyolefine isolating film base material;
(4) high-temperature baking removes moisture, and one or both formation nano-scale coatings of described nanoscale zirconia, aluminium oxide, silica, silicon nitride, aluminium nitride are also attached on described barrier film base material by described Lithium acrylate and acrylonitrile copolymer.
After the present invention has taked such scheme, due to the Lithium acrylate adopting and the aqueous dispersions of acrylonitrile copolymer, adopt deionized water as solvent simultaneously, production process is simple, can not discharge the toxic gas that has pollution to environment, also there is no disaster hidden-trouble, and, Lithium acrylate and acrylonitrile copolymer have very high electrochemical stability, though voltage reach 4.5V can be not oxidized and decompose yet, therefore guarantee to use the battery of its making to possess long term reliability and fail safe.
Other features and advantages of the present invention will be set forth in the following description, and, partly from specification, become apparent, or understand by implementing the present invention.Object of the present invention and other advantages can be realized and be obtained by specifically noted structure in write specification, claims and accompanying drawing.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is described in detail, to make above-mentioned advantage of the present invention clearer and more definite.Wherein,
Fig. 1 is the structural representation of barrier film for the lithium rechargeable battery of the embodiment of the present invention.
Embodiment
Describe embodiments of the present invention in detail below with reference to drawings and Examples, to the present invention, how application technology means solve technical problem whereby, and the implementation procedure of reaching technique effect can fully understand and implement according to this.It should be noted that, only otherwise form conflict, each feature in each embodiment and each embodiment in the present invention can mutually combine, and the technical scheme forming is all within protection scope of the present invention.
As shown in Figure 1, described lithium rechargeable battery barrier film, comprise the base material 1 of polyolefine isolating film, the one or both sides of the base material of described polyolefine isolating film are coated with one or both nano coatings that form 2 in zirconia, aluminium oxide, silica, silicon nitride, aluminium nitride.
Wherein, in an embodiment, the base material of described nano coating and described polyolefine isolating film is bonded together by Lithium acrylate and acrylonitrile copolymer.
In actual product, can not obviously find out its difference due to Lithium acrylate and acrylonitrile copolymer and described nano coating, therefore, not mark in the drawings.
Wherein, in an embodiment, the thickness of described nano coating is at 2-5 micron.
And the molecular weight of described Lithium acrylate and acrylonitrile copolymer is between 600,000～2,500,000.
After the present invention has taked such scheme, due to the Lithium acrylate adopting and the aqueous dispersions of acrylonitrile copolymer, adopt deionized water as solvent simultaneously, production process is simple, can not discharge the toxic gas that has pollution to environment, also there is no disaster hidden-trouble, and, Lithium acrylate and acrylonitrile copolymer have very high electrochemical stability, though voltage reach 4.5V can be not oxidized and decompose yet, therefore guarantee to use the battery of its making to possess long term reliability and fail safe.
Below in conjunction with specific embodiment, preparation method of the present invention is described, mainly comprises following several key steps, be summarized as follows:
(1) aqueous dispersions of Lithium acrylate and acrylonitrile copolymer is added in deionized water;
(2) one or both in interpolation nanoscale zirconia, aluminium oxide, silica, silicon nitride, aluminium nitride, stir and grind;
(3) one or both of described nanoscale zirconia after treatment step (2), aluminium oxide, silica, silicon nitride, aluminium nitride are attached in a side or two sides of polyolefine isolating film base material;
(4) high-temperature baking removes moisture, and one or both formation nano-scale coatings of described nanoscale zirconia, aluminium oxide, silica, silicon nitride, aluminium nitride are also attached on described barrier film base material by described Lithium acrylate and acrylonitrile copolymer.
Wherein, according to different embodiment, in step (1), the weight content of described Lithium acrylate and acrylonitrile copolymer is at 0.5%-20%.
Wherein, according to different embodiment, in step (2), the weight content of described nanoscale zirconia, aluminium oxide, silica, silicon nitride, aluminium nitride is at 2%-30%.
Wherein, according to different embodiment, in step (3), described deionized water is attached in a side or two sides of polyolefine isolating film base material by the mode of spraying, immersion or directly coating.
And, to process and exhale by said method, described nanometer layer is attached on the barrier film of polyolefine isolating film base material, forms the lithium rechargeable battery barrier film of high security.
After the present invention has taked such scheme, due to the Lithium acrylate adopting and the aqueous dispersions of acrylonitrile copolymer, adopt deionized water as solvent simultaneously, production process is simple, can not discharge the toxic gas that has pollution to environment, also there is no disaster hidden-trouble, and, Lithium acrylate and acrylonitrile copolymer have very high electrochemical stability, though voltage reach 4.5V can be not oxidized and decompose yet, therefore guarantee to use the battery of its making to possess long term reliability and fail safe.
It should be noted that, for said method embodiment, for simple description, therefore it is all expressed as to a series of combination of actions, but those skilled in the art should know, the application is not subject to the restriction of described sequence of movement, because according to the application, some step can adopt other orders or carry out simultaneously.Secondly, those skilled in the art also should know, the embodiment described in specification all belongs to preferred embodiment, and related action and module might not be that the application is necessary.
Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (8)
1. a lithium rechargeable battery barrier film, it is characterized in that, comprise the base material of polyolefine isolating film, the one or both sides of the base material of described polyolefine isolating film are coated with one or both nano coatings that form in zirconia, aluminium oxide, silica, silicon nitride, aluminium nitride.
2. lithium rechargeable battery barrier film according to claim 1, is characterized in that, the thickness of described nano coating is at 2-5 micron.
3. lithium rechargeable battery barrier film according to claim 1 and 2, is characterized in that, the base material of described nano coating and described polyolefine isolating film is bonded together by Lithium acrylate and acrylonitrile copolymer.
4. lithium rechargeable battery barrier film according to claim 3, is characterized in that, it is characterized in that, the molecular weight of described Lithium acrylate and acrylonitrile copolymer is between 600,000～2,500,000.
5. a preparation method for barrier film for lithium rechargeable battery, is characterized in that, comprising:
(1) aqueous dispersions of Lithium acrylate and acrylonitrile copolymer is added in deionized water;
(2) one or both in interpolation nanoscale zirconia, aluminium oxide, silica, silicon nitride, aluminium nitride, dispersed with stirring is even;
(3) one or both of described nanoscale zirconia after treatment step (2), aluminium oxide, silica, silicon nitride, aluminium nitride are attached in a side or two sides of polyolefine isolating film base material;
(4) high-temperature baking removes moisture, and one or both formation nano-scale coatings of described nanoscale zirconia, aluminium oxide, silica, silicon nitride, aluminium nitride are also attached on described barrier film base material by described Lithium acrylate and acrylonitrile copolymer.
6. the preparation method of barrier film for lithium rechargeable battery according to claim 5, is characterized in that, in step (1), the weight content of described Lithium acrylate and acrylonitrile copolymer is at 0.5%-20%.
7. the preparation method of barrier film for lithium rechargeable battery according to claim 5, is characterized in that, in step (2), the weight content of described nanoscale zirconia, aluminium oxide, silica, silicon nitride, aluminium nitride is at 2%-30%.
8. the preparation method of barrier film for lithium rechargeable battery according to claim 5, it is characterized in that, in step (3), described deionized water is attached in a side or two sides of polyolefine isolating film base material by the mode of spraying, immersion or directly coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210444056.7A CN103811699A (en) | 2012-11-08 | 2012-11-08 | Isolation film for lithium ion secondary battery, and making method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210444056.7A CN103811699A (en) | 2012-11-08 | 2012-11-08 | Isolation film for lithium ion secondary battery, and making method thereof |
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| CN103811699A true CN103811699A (en) | 2014-05-21 |
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| CN201210444056.7A Pending CN103811699A (en) | 2012-11-08 | 2012-11-08 | Isolation film for lithium ion secondary battery, and making method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023098044A1 (en) * | 2021-12-01 | 2023-06-08 | 上海恩捷新材料科技有限公司 | Heat-conducting lithium ion separator and preparation method therefor |
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| US20060141352A1 (en) * | 2004-03-30 | 2006-06-29 | Kiyomi Kato | Lithium ion secondary battery and charging method therefor, and charge or charge/discharge control system for lithium ion secondary battery |
| CN101212036A (en) * | 2007-12-21 | 2008-07-02 | 成都中科来方能源科技有限公司 | Microporous polymer isolating film for Li-ion battery and method for producing the same |
| CN101861667A (en) * | 2007-11-19 | 2010-10-13 | 株式会社Lg化学 | Separator having porous coating layer and electrochemical device containing the same |
| CN102306725A (en) * | 2011-08-04 | 2012-01-04 | 东莞新能源科技有限公司 | Lithium ion battery |
| CN102437302A (en) * | 2011-11-25 | 2012-05-02 | 东莞市比比克电子科技有限公司 | Lithium ion battery diaphragm and high temperature thermal-stable lithium ion battery |
| CN102522516A (en) * | 2011-12-22 | 2012-06-27 | 中国科学院青岛生物能源与过程研究所 | Asymmetric composite diaphragm for lithium ion secondary cell and preparation method thereof |
| CN102738427A (en) * | 2012-07-19 | 2012-10-17 | 河南义腾新能源科技有限公司 | Inorganic composite microporous membrane serving as lithium ion battery diaphragm and preparation method thereof |
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2012
- 2012-11-08 CN CN201210444056.7A patent/CN103811699A/en active Pending
Patent Citations (7)
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| US20060141352A1 (en) * | 2004-03-30 | 2006-06-29 | Kiyomi Kato | Lithium ion secondary battery and charging method therefor, and charge or charge/discharge control system for lithium ion secondary battery |
| CN101861667A (en) * | 2007-11-19 | 2010-10-13 | 株式会社Lg化学 | Separator having porous coating layer and electrochemical device containing the same |
| CN101212036A (en) * | 2007-12-21 | 2008-07-02 | 成都中科来方能源科技有限公司 | Microporous polymer isolating film for Li-ion battery and method for producing the same |
| CN102306725A (en) * | 2011-08-04 | 2012-01-04 | 东莞新能源科技有限公司 | Lithium ion battery |
| CN102437302A (en) * | 2011-11-25 | 2012-05-02 | 东莞市比比克电子科技有限公司 | Lithium ion battery diaphragm and high temperature thermal-stable lithium ion battery |
| CN102522516A (en) * | 2011-12-22 | 2012-06-27 | 中国科学院青岛生物能源与过程研究所 | Asymmetric composite diaphragm for lithium ion secondary cell and preparation method thereof |
| CN102738427A (en) * | 2012-07-19 | 2012-10-17 | 河南义腾新能源科技有限公司 | Inorganic composite microporous membrane serving as lithium ion battery diaphragm and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023098044A1 (en) * | 2021-12-01 | 2023-06-08 | 上海恩捷新材料科技有限公司 | Heat-conducting lithium ion separator and preparation method therefor |
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Application publication date: 20140521 |
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