CN102354733B - Method for making lithium ion battery diaphragm by ion template effect - Google Patents
Method for making lithium ion battery diaphragm by ion template effect Download PDFInfo
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- CN102354733B CN102354733B CN2011102433988A CN201110243398A CN102354733B CN 102354733 B CN102354733 B CN 102354733B CN 2011102433988 A CN2011102433988 A CN 2011102433988A CN 201110243398 A CN201110243398 A CN 201110243398A CN 102354733 B CN102354733 B CN 102354733B
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- polyimide film
- ion battery
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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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Abstract
The invention relates to a lithium ion battery technology and aims at providing a method for making a lithium ion battery diaphragm by ion template effect. The method comprises the following steps of: adding lithium carbonate with the same molar with benzidine after reacting the benzidine, aromatic anhydride and N, N-dimethyl acetyl amide, and then agitating until uniformly mixing for reaction; after casting the mixture into a film, removing residual N, N-dimethyl acetyl amide, and then heating the film for decarboxylation and dehydration to make a polyimide film containing lithium oxide; repeatedly extracting with a thin hydrate solution to remove the lithium oxide, and obtaining the porous polyimide film with uniform lithium ion bore diameters. The invention has the advantages that the bore diameters of the film can be effectively controlled in the diameter range of lithium ions, the bore diameter distribution and the bore clearance rate are uniform, uniform transmission speed of the lithium ions between a positive electrode and a negative electrode and quantitive lithium ion transmission are ensured in the electrochemical charge and discharge process of the battery, the discharge capacity of the battery is stable, and the cycle service life is prolonged.
Description
Technical field
The present invention relates to the lithium-ion electric pool technology, particularly utilize ion masterplate effect to prepare the method for lithium ion battery separator.
Background technology
Since early 1990s, Sony was succeeded in developing lithium ion battery, lithium ion battery was high with its energy density, have extended cycle life and the electrical property of the high excellence of voltage and obtain to develop rapidly.Be widely used at present the electronic product such as mobile phone, portable computer, camera, video camera field, and application is still among continuous expansion.Lithium ion battery is comprised of both positive and negative polarity, electrolyte and barrier film.Wherein, a critical function of barrier film is the isolation both positive and negative polarity and stops the interior electronics of battery to pass, can allow passing through of ion simultaneously, thereby complete the fast transport of lithium ion between both positive and negative polarity in the charge discharge process.The quality of membrane properties directly affects discharge capacity and the service life cycle of battery, therefore need to give enough attention to research and the application of diaphragm material.
At present, barrier film with the preparation method of microporous barrier can be divided into dry method (fusion drawn, MSCS) and wet method (thermic is separated, TIPS) two kinds.Two kinds of methods comprise that all at least one orientation step makes film produce hole and improve hot strength.
The technological deficiency that above-mentioned two kinds of methods exist is: in the orientation stretching thin-film process, the aperture of film, pore-size distribution and porosity are difficult to control evenly, cause in battery in the charge discharge process the inhomogeneous and lithium ion of lithium ion transmission speed between both positive and negative polarity quantitatively transmission had a strong impact on, directly affect discharge capacity and the service life cycle of battery.The present invention can overcome the deficiency in above-mentioned two kinds of method and technologies, and the aperture that can effectively control film is even in lithium ion diameter range, pore-size distribution and porosity.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes deficiency of the prior art, and a kind of method of utilizing ion masterplate effect to prepare lithium ion battery separator is provided.
Be the technical solution problem, solution of the present invention is:
A kind of method of utilizing ion masterplate effect to prepare lithium ion battery separator is provided, comprises the following steps:
(1) be that 1: 1: 26～52 benzidine, aromatic anhydride, DMA add in reactor successively with mol ratio, then reaction 2 hours under 70～90 ℃ of conditions;
(2) add benzidine to equate the lithium carbonate of molal quantity in reaction system, then stir to make to mix and react;
(3) with after the mixture casting film, remove remaining DMA under 70～90 ℃ of conditions, then film is warmed up to the polyimide film that oxide containing lithium is made in 150～220 ℃ of lower decarboxylations and dehydration;
(4) polyimide film is extracted to remove lithia repeatedly with diluted hydrochloric acid aqueous solution, obtain having the porous polyimide film in uniform lithium ion aperture;
(5) oven dry film, cutting obtains the lithium ion battery separator finished product.
In the present invention, the thickness of described porous polyimide film is 30～100 μ m.
In the present invention, the time of stirring described in described step (2) is 2 hours.
In the present invention, described aromatic anhydride is pyromellitic dianhydride, biphenyl tetracarboxylic acid anhydrides, bibenzene tetracarboxylic ether acid anhydride or bibenzene tetracarboxylic ketone acid anhydride.
The invention has the beneficial effects as follows:
This patent adopts the means of Polymer Synthesizing, innovates from the generation of membrane material, membrane preparation method, membrane aperture and the uniformity of membrane aperture comprehensively.With respect to membrane material preparation method of the prior art, technique effect of the present invention is: can make film effectively control the aperture even in lithium ion diameter range, pore-size distribution and porosity, cause in battery in the charge discharge process lithium ion between both positive and negative polarity transmission speed all even lithium ion quantitatively transmit, the stable and service life cycle of the discharge capacity of battery is extended.
Embodiment
Embodiment 1:
184 gram benzidines and 218 gram pyromellitic dianhydrides, 2278 gram DMAs are warming up to 70 ℃ of reactions 5 hours in reactor, add 67 gram lithium carbonates in reactor, stir 2 hours; With the product casting film, film is removed DMA at 80 ℃; Then film is warmed up to 150 ℃ of decarboxylations and dehydration and makes the polyimide film of oxide containing lithium, the thickness of film is 30 μ m.Film is extracted repeatedly with diluted hydrochloric acid aqueous solution, remove lithia, the oven dry film cuts into finished product.
Embodiment 2:
184 gram benzidines and 294 gram biphenyl tetracarboxylic acid anhydrides, 4302 gram DMAs are warming up to 80 ℃ of reactions 5 hours in reactor, add 67 gram lithium carbonates in reactor, stir 2 hours; With the product casting film, film is removed DMA at 70 ℃; Then film is warmed up to 170 ℃ of decarboxylations and dehydration and makes the polyimide film of oxide containing lithium, the thickness of film is 50 μ m.Film is extracted repeatedly with diluted hydrochloric acid aqueous solution, remove lithia, the oven dry film cuts into finished product.
Example 3:
184 gram benzidines and 310 gram bibenzene tetracarboxylic ether acid anhydrides, 4446 gram DMAs temperature in reactor rises to 90 ℃ of reactions 5 hours, adds 67 gram lithium carbonates in reactor, stirred 2 hours; With the product casting film, film is removed DMA at 90 ℃; Then film is warmed up to 190 ℃ of decarboxylations and dehydration and makes the polyimide film of oxide containing lithium, the thickness of film is 85 μ m.Film is extracted repeatedly with diluted hydrochloric acid aqueous solution, remove lithia, the oven dry film cuts into finished product.
Example 4:
184 gram benzidines and 322 gram bibenzene tetracarboxylic ketone acid anhydrides, 4554 gram DMAs are warming up to 85 ℃ of reactions 5 hours in reactor, add 67 gram lithium carbonates in reactor, stir 2 hours; With the product casting film, film is removed DMA at 85 ℃; Then film is warmed up to 220 ℃ of decarboxylations and dehydration and makes the polyimide film of oxide containing lithium, the thickness of film is 100 μ m.Film is extracted repeatedly with diluted hydrochloric acid aqueous solution, remove lithia, the oven dry film cuts into finished product.
At last, it is also to be noted that, what more than enumerate is only some specific embodiment of the present invention.Obviously, the invention is not restricted to above examples of implementation, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (4)
1. method of utilizing ion masterplate effect to prepare lithium ion battery separator comprises the following steps:
(1) be that 1: 1: 26～52 benzidine, aromatic anhydride, DMA add in reactor successively with mol ratio, then reaction 5 hours under 70～90 ℃ of conditions;
(2) add the lithium carbonate that equates molal quantity with benzidine in reaction system, then stir to make to mix and react;
(3) with after the mixture casting film, remove remaining DMA under 70～90 ℃ of conditions, then film is warmed up to the polyimide film that oxide containing lithium is made in 150～220 ℃ of lower decarboxylations and dehydration;
(4) polyimide film is extracted to remove lithia repeatedly with diluted hydrochloric acid aqueous solution, obtain having the porous polyimide film in uniform lithium ion aperture;
(5) oven dry film, cutting obtains the lithium ion battery separator finished product.
2. method according to claim 1, is characterized in that, the thickness of described porous polyimide film is 30～100 μ m.
3. method according to claim 1, is characterized in that, the time of stirring described in described step (2) is 2 hours.
4. method according to claim 1, is characterized in that, described aromatic anhydride is pyromellitic dianhydride, biphenyl tetracarboxylic acid anhydrides, bibenzene tetracarboxylic ether acid anhydride or bibenzene tetracarboxylic ketone acid anhydride.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102433988A CN102354733B (en) | 2011-08-23 | 2011-08-23 | Method for making lithium ion battery diaphragm by ion template effect |
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| CN2011102433988A CN102354733B (en) | 2011-08-23 | 2011-08-23 | Method for making lithium ion battery diaphragm by ion template effect |
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| CN102354733A CN102354733A (en) | 2012-02-15 |
| CN102354733B true CN102354733B (en) | 2013-11-06 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103383996B (en) * | 2013-06-27 | 2015-07-22 | 江苏华东锂电技术研究院有限公司 | Preparation method of polyimide micro-pore diaphragm |
| CN106410093A (en) * | 2016-10-20 | 2017-02-15 | 常州市鼎日环保科技有限公司 | Preparation method of lithium-ion battery composite separator |
| CN110707312A (en) * | 2019-11-06 | 2020-01-17 | 联动天翼新能源有限公司 | Production process of modified polyimide coated ternary material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101645497A (en) * | 2008-08-05 | 2010-02-10 | 比亚迪股份有限公司 | Polyimide porous membrane, preparation method thereof and lithium ion battery |
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| CN101645497A (en) * | 2008-08-05 | 2010-02-10 | 比亚迪股份有限公司 | Polyimide porous membrane, preparation method thereof and lithium ion battery |
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