CN104183807A - Method for modifying PE film and PTFE film composite membrane for lithium ion battery - Google Patents
Method for modifying PE film and PTFE film composite membrane for lithium ion battery Download PDFInfo
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- CN104183807A CN104183807A CN201410412698.8A CN201410412698A CN104183807A CN 104183807 A CN104183807 A CN 104183807A CN 201410412698 A CN201410412698 A CN 201410412698A CN 104183807 A CN104183807 A CN 104183807A
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- film
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- composite membrane
- ptfe film
- lithium ion
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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
- H01M50/411—Organic material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/02—Chemical treatment or coating of shaped articles made of macromolecular substances with solvents, e.g. swelling agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- 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 invention relates to a method for modifying a PE film and PTFE film composite diaphragm for a lithium ion battery. The method for modifying the PE film and PTFE film composite diaphragm for the lithium ion battery is characterized by comprising the following steps: (1) infiltrating a PE film in a modifying solution; (2) taking out the infiltrated PE film obtained in the step (1), and compounding the infiltrated PE film with a PTFE film by virtue of a multi-roller compounding device; (3) taking out the PE film and PTFE film composite membrane, and drying the PE film and PTFE film composite membrane in an airtight and clean constant temperature drying oven; (4) stretching the dried PE film and PTFE film composite membrane obtained in the step (3) on a multi-roller stretching device; (5) extracting the stretched PE film and PTFE film composite membrane obtained in the step (4) in an extraction device; (6) carrying out forced air drying on the extracted PE film and PTFE film composite membrane obtained in the step (5) in a constant temperature forced air drying device, and finally cutting to obtain the finished product, namely the modified PE film and PTFE film composite membrane for the lithium ion battery. The method provided by the invention is applicable to the PE film and PTFE film composite membrane for the lithium ion battery.
Description
Technical field
The present invention relates to the composite diaphragm of PE film and PTFE film for a kind of lithium ion battery, particularly relate to a kind of method of the composite diaphragm modification of PE film and PTFE film for lithium ion battery.
Background technology
The barrier film that lithium ion battery is conventional is PE film, but due to the factor of the chemical physical property of PE film itself, using it as lithium ion battery barrier film, its fail safe cannot guarantee, especially in high-power lithium ion battery field, barrier film by PE film as lithium ion battery, its closed pore temperature is lower, when temperature slightly rises, will upset ion current, this phenomenon can affect the normal work of battery, if closed pore temperature is too high, will cause the serious accidents such as lithium ion battery blast on fire.Therefore lithium ion battery separator also should have heat resistance, and barrier film should be able to maintain closed pore state and indeformable until the temperature that certain is higher after closed pore always.Lithium ion battery separator also has a film to break temperature simultaneously, if membrane ruptures, positive and negative electrode will directly contact and explode, this is also breakneck, so lithium ion battery separator should have enough heat resistances, make barrier film at it, more than melt temperature keep its shape, to maintain closed pore situation to high as far as possible temperature as far as possible.
Be generally to reach and improve the durothermic object of barrier film for lithium ion battery, and PE film and resistant to elevated temperatures PTFE film is compound, to form composite diaphragm for lithium ion battery.But because the feature of the molecular structure of PTFE itself determines, the wettability of this composite diaphragm for lithium ion battery will be greatly affected, and by the lithium ion battery of PE film and the compound rear preparation of resistant to elevated temperatures PTFE film, by its battery capacity of diaphragm cell group and battery efficiency, will be greatly affected.
Need by PE film and the compound lithium ion battery of PTFE film are carried out to modification with barrier film for this reason.Yet conventional chemical modification method is easy to destroy physical property and the chemical property of product itself, and the problem of environmental pollution easily causing because use various chemical substances.Concrete method of modifying comprises plasma treatment, surfactant processing, hydrophilic polymer coating and graft modification etc.Plasma treatment can effectively be improved the wettability of microporous barrier at surperficial polarization group, and still, energetic plasma is processed and easily caused polymer pore structure to destroy, and expensive equipment has also limited its large-scale application.It is amphipathic for surfactant processing and utilizing, and hydrophobic side is adsorbed in to apolar surfaces, and water-wet side is contacted with polarizable medium, can improve the wettability of dewatering microporous film, still, SURFACTANT ADSORPTION amount is few, DeGrain, and hydrophobic interaction is weak interaction, unstable.Hydrophilic polymer applies and exists adhesion not strong, easily causes the defect of blockage of the micro orifice.Graft modification needs starvation, and carries out under high temperature or high energy initiation, and equipment requirement is high, also easily causes plug-hole.
Summary of the invention
The object of the invention is to provide the method for a kind of lithium ion battery with the composite diaphragm modification of PE film and PTFE film, the wettability with the composite diaphragm that improves PE film and PTFE film to electrolyte.
Solution of the present invention is to achieve the above object: lithium ion battery of the present invention is as follows by the operating procedure of the method for the composite diaphragm modification of PE film and PTFE film:
1) PE film is infiltrated in modified solution, infiltration temperature is 35-85 ℃, and infiltrating time is 10-60min, makes PE film obtain sufficient effect of impregnation, and the content of the modified solution in the PE film after the infiltrating 10-55% that is total adsorbance, modified solution is any one or its mixed solution in paraffin oil, benzinum, gasoline, aviation kerosine, in its mixed solution, and meter by weight, paraffin oil 15-20 part, benzinum 25-32 part, gasoline 25-40 part, aviation kerosine 35-50 part;
2) by above-mentioned steps 1) PE film after infiltrating takes out, and compound by multiple roll set composite with PTFE film, combinational environment temperature is 65-125 ℃, and composite pressure is 0.05-20MPa, and the rotating speed of composite roll is 0.1-10m/min;
3) by above-mentioned steps 2) composite membrane of PE film and PTFE film takes out, and dry in the thermostatic drying chamber of airtight cleaning, initial baking temperature is 35-65 ℃, with 0.5 ℃/min programming rate, rise to 65-125 ℃, freeze-day with constant temperature, the freeze-day with constant temperature time is 10-3000min;
4) by above-mentioned steps 3) composite membrane of dried PE film and PTFE film is positioned on multiple roll stretching device and stretches, and draft temperature is 35-95 ℃, draw ratio 1: 1.2-1: 5;
5) by above-mentioned steps 4) the PE film after stretching and the composite membrane of PTFE film be positioned in extraction equipment and extract, extraction ambient temperature is 25-45 ℃, extraction time is 5-90min, extractant is any one or its mixed solution in ethanol, acetone, poly-trichloroethylene, nitrogen dimethylformamide, nitrogen nitrogen dimethylacetylamide, its mixed solution is counted ethanol 5-15 part by weight, acetone 18-32 part, poly-trichloroethylene 21-40 part, nitrogen dimethylformamide 25-49 part, nitrogen nitrogen dimethylacetylamide 30-50 part;
6) by above-mentioned steps 5) the PE film after having extracted and the composite membrane of PTFE film be positioned over and in constant temperature forced air drying device, carry out forced air drying, forced air drying temperature 45-100 ℃, air blast wind speed is 100-1500rpm, the forced air drying processing time is 25-125min, finally be cut into finished product, make the compound lithium ion battery barrier film of the PE film of modification and PTFE film.
The method of the composite diaphragm modification of PE film and PTFE film and the method for employing physical modification for lithium ion battery of the present invention, compound, dry, the stretching of the main infiltration by PE film, the PE film after infiltrating and PTFE film, extraction, forced air drying and cutting, finally make the compound lithium ion battery barrier film of the PE film of modification and PTFE film, and changed the physical structure of barrier film, thereby reach, reduce product internal resistance, improve the object of coulomb efficiency.
Comparative result before and after modification is in Table one.
Table one
The method of modification of the present invention is suitable for the composite diaphragm application of PE film and PTFE film for lithium ion battery.
Accompanying drawing explanation
Lithium ion battery of the present invention is provided by following embodiment and accompanying drawing thereof by the method for the composite diaphragm modification of PE film and PTFE film.
Fig. 1 is the schematic flow sheet of the method for the composite diaphragm modification of PE film and PTFE film for lithium ion battery of the present invention.
Embodiment
Below with reference to accompanying drawing, lithium ion battery of the present invention is described in further detail by the method for the composite diaphragm modification of PE film and PTFE film.
PE film used is commercially available conventional micro-pore septum for lithium ion battery, and its gas permeability is 110-250 sec/100 ㏄, and porosity is 30-65%, and percent thermal shrinkage is 0.5-7%, and piercing through intensity is 300-800gf, and hot strength is 0.05-20MPa.
PTFE film used is commercially available conventional micro-pore septum for lithium ion battery, and its aperture is between 0.08-2.5 μ m, and fabric width is 0.8-2.75m, and thickness is 10-50um, and porosity is 65% ~ 85%, and hot strength is >=20MPa.
Referring to Fig. 1, the lithium ion battery of this invention is poly-as follows by the operation step of the method for the composite diaphragm modification of PE film and PTFE film:
1) PE film is infiltrated in modified solution, and it is that 15 paraffin oils, parts by weight are that 25 benzinums, parts by weight are that 30 gasoline and parts by weight are the mixed and modified solution that 39 aviation kerosines form by parts by weight, infiltrating time is 56min, make PE film obtain sufficient effect of impregnation, the content of the modified solution in the PE film after infiltration is total adsorbance 13%;
2) by above-mentioned steps 1) PE film after infiltrating takes out, and compound by multiple roll set composite with PTFE film, combinational environment temperature is 120 ℃, and composite pressure is 1.3MPa, and the rotating speed of composite roll is 1m/min;
3) by above-mentioned steps 2) composite membrane of PE film and PTFE film takes out, and is placed in the thermostatic drying chamber of airtight cleaning dryly, and initial baking temperature is 60 ℃, with 0.5 ℃/min programming rate, rises to 90 ℃, then freeze-day with constant temperature 100min;
4) by above-mentioned steps 3) composite membrane of dried PE film and PTFE film is positioned on multiple roll stretching device and stretches, and draft temperature is 75 ℃, and draw ratio is 1: 3;
5) by above-mentioned steps 4) the PE film after stretching is positioned in extraction tank and extracts with the composite membrane of PTFE film, and extractant is acetone soln, and extracting ambient temperature is 35 ℃, and extraction time is 6min;
6) by above-mentioned steps 5) the PE film after having extracted and the composite membrane of PTFE film be positioned over and in constant temperature forced air drying device, carry out forced air drying, forced air drying temperature is 78 ℃, air blast wind speed is 500rpm, the forced air drying processing time is 30min, finally be cut into finished product, make the compound lithium ion battery barrier film of the PE film of modification and PTFE film.
Claims (1)
1. a method for the composite diaphragm modification of PE film and PTFE film for lithium ion battery, is characterized in that the operating procedure of the method is as follows:
1) PE film is infiltrated in modified solution, infiltration temperature is 35-85 ℃, and infiltrating time is 10-60min, makes PE film obtain sufficient effect of impregnation, and the content of the modified solution in the PE film after the infiltrating 10-55% that is total adsorbance, modified solution is any one or its mixed solution in paraffin oil, benzinum, gasoline, aviation kerosine, in its mixed solution, and meter by weight, paraffin oil 15-20 part, benzinum 25-32 part, gasoline 25-40 part, aviation kerosine 35-50 part;
2) by above-mentioned steps 1) PE film after infiltrating takes out, and compound by multiple roll set composite with PTFE film, combinational environment temperature is 65-125 ℃, and composite pressure is 0.05-20MPa, and the rotating speed of composite roll is 0.1-10m/min;
3) by above-mentioned steps 2) composite membrane of PE film and PTFE film takes out, and dry in the thermostatic drying chamber of airtight cleaning, initial baking temperature is 35-65 ℃, with 0.5 ℃/min programming rate, rise to 65-125 ℃, freeze-day with constant temperature, the freeze-day with constant temperature time is 10-3000min;
4) by above-mentioned steps 3) composite membrane of dried PE film and PTFE film is positioned on multiple roll stretching device and stretches, and draft temperature is 35-95 ℃, draw ratio 1: 1.2-1: 5;
5) by above-mentioned steps 4) the PE film after stretching and the composite membrane of PTFE film be positioned in extraction equipment and extract, extraction ambient temperature is 25-45 ℃, extraction time is 5-90min, extractant is any one or its mixed solution in ethanol, acetone, poly-trichloroethylene, nitrogen dimethylformamide, nitrogen nitrogen dimethylacetylamide, its mixed solution is counted ethanol 5-15 part by weight, acetone 18-32 part, poly-trichloroethylene 21-40 part, nitrogen dimethylformamide 25-49 part, nitrogen nitrogen dimethylacetylamide 30-50 part;
6) by above-mentioned steps 5) the PE film after having extracted and the composite membrane of PTFE film be positioned over and in constant temperature forced air drying device, carry out forced air drying, forced air drying temperature 45-100 ℃, air blast wind speed is 100-1500rpm, the forced air drying processing time is 25-125min, finally be cut into finished product, make the compound lithium ion battery barrier film of the PE film of modification and PTFE film.
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| CN201410412698.8A CN104183807B (en) | 2014-08-21 | 2014-08-21 | The lithium ion battery method of PE film with the composite diaphragm modification of PTFE film |
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| CN201410412698.8A CN104183807B (en) | 2014-08-21 | 2014-08-21 | The lithium ion battery method of PE film with the composite diaphragm modification of PTFE film |
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| CN104183807B CN104183807B (en) | 2016-09-28 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107478546A (en) * | 2017-07-10 | 2017-12-15 | 合肥国轩高科动力能源有限公司 | A kind of method of lithium battery diaphragm wellability test |
| CN116925422A (en) * | 2023-09-18 | 2023-10-24 | 国家电投集团氢能科技发展有限公司 | Polytetrafluoroethylene membrane and preparation method thereof, expanded polytetrafluoroethylene and composite ion exchange membrane and application thereof |
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| CN101469078A (en) * | 2007-12-26 | 2009-07-01 | Sk能源 | Microporous polyolefin multi layer film and preparing method thereof |
| CN103187549A (en) * | 2011-12-28 | 2013-07-03 | 山东东岳高分子材料有限公司 | Diaphragm for lithium ion battery and preparation method thereof |
| CN103524778A (en) * | 2013-09-22 | 2014-01-22 | 佛山市金辉高科光电材料有限公司 | Modified pore-foaming agent and preparation method and application thereof to lithium ion battery diaphragm |
| KR20140071095A (en) * | 2012-12-03 | 2014-06-11 | 주식회사 엘지화학 | High permeable polyethylene separator, and preparation method thereof |
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2014
- 2014-08-21 CN CN201410412698.8A patent/CN104183807B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101001904A (en) * | 2004-06-11 | 2007-07-18 | Sk株式会社 | Microporous high density polyethylene film and method of producing the same |
| CN101469078A (en) * | 2007-12-26 | 2009-07-01 | Sk能源 | Microporous polyolefin multi layer film and preparing method thereof |
| CN103187549A (en) * | 2011-12-28 | 2013-07-03 | 山东东岳高分子材料有限公司 | Diaphragm for lithium ion battery and preparation method thereof |
| KR20140071095A (en) * | 2012-12-03 | 2014-06-11 | 주식회사 엘지화학 | High permeable polyethylene separator, and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107478546A (en) * | 2017-07-10 | 2017-12-15 | 合肥国轩高科动力能源有限公司 | A kind of method of lithium battery diaphragm wellability test |
| CN116925422A (en) * | 2023-09-18 | 2023-10-24 | 国家电投集团氢能科技发展有限公司 | Polytetrafluoroethylene membrane and preparation method thereof, expanded polytetrafluoroethylene and composite ion exchange membrane and application thereof |
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| CN104183807B (en) | 2016-09-28 |
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