CN103524778A - Modified pore-foaming agent and preparation method and application thereof to lithium ion battery diaphragm - Google Patents
Modified pore-foaming agent and preparation method and application thereof to lithium ion battery diaphragm Download PDFInfo
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- CN103524778A CN103524778A CN201310432963.4A CN201310432963A CN103524778A CN 103524778 A CN103524778 A CN 103524778A CN 201310432963 A CN201310432963 A CN 201310432963A CN 103524778 A CN103524778 A CN 103524778A
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a modified pore-foaming agent which is formed by polymerizing paroline and polar monomer through free radicals, wherein the weight ratio of the paroline to the unsaturated polar monomer to a free radical initiator is 100:(0.5-2):(0.5-1); and the paroline, the unsaturated polar monomer, the free radical initiator and polyolefin are processed into a lithium ion battery diaphragm, thus the gas permeability, the wettability and the capacity of absorbing electrolyte of the lithium ion battery diaphragm are improved, and thus the purpose of increasing the battery capacity is reached, and the requirement of a large-power battery is met.
Description
Technical field
The present invention relates to technical field of lithium ion, be specifically related to a kind of modification pore-creating agent and preparation method thereof application in lithium ion battery separator with it.
Background technology
Lithium ion battery separator is that the isolation positive and negative electrode that plays being applied in lithium ion battery prevents that battery short circuit has certain pore texture simultaneously and can guarantee one of significant components of the lithium ion battery that lithium ion passes through smoothly.
Along with lithium ion cell high-capacity, high-power development trend, the performance of lithium ion battery separator is also required to improve constantly, and high-end lithium ion battery especially diaphragm of power lithium ion battery requires to have larger pore texture and electrolytic solution receptivity simultaneously.Guaranteeing under the prerequisite of security, larger pore texture is conducive to lithium ion fast by barrier film, improves the power of lithium ion battery.Good electrolytic solution receptivity is conducive to the raising of the liquid storage ability of barrier film, improves cell container.
In Chinese patent application CN1310483, disclose polymer-coated in conventional liquid lithium ionic cell barrier film, obtain modified diaphragm, polymeric coating in modified diaphragm, as PVDF coating can improve electrolytic solution receptivity and the hold facility of barrier film, improve capacity and imbibition ability and the high temperature safety of battery.But the method for this modification can not improve the porosity of battery diaphragm, cannot meet the requirement of the larger power of battery.
Summary of the invention
For overcoming the defect of prior art, be of the present inventionly to provide a kind of modification pore-creating agent, for the preparation of lithium ion battery separator, to improve the ventilation property of battery diaphragm, meet the requirement of high power battery.
Another object of the present invention is to provide a kind of preparation method of above-mentioned modification pore-creating agent.
The 3rd object of the present invention is above-mentioned modification pore-creating agent to be applied in lithium ion battery separator.
The 4th object of the present invention is to provide a kind of lithium ion battery separator that comprises above-mentioned modification pore-creating agent, to improve the ability of ventilation property, wetting property and the Electolyte-absorptive of lithium ion battery separator, thereby reaches the object that improves cell container.
The 5th object of the present invention is to provide a kind of preparation method of above-mentioned lithium ion battery separator.
The technical solution adopted in the present invention is as follows for achieving the above object:
A pore-creating agent, it is to be formed by radical polymerization by paraffin oil and polar monomer, in reaction, wherein the mass ratio of paraffin oil, unsaturated polar monomer and radical initiator is 100:(0.5-2): (0.5-1).
The paraffin oil adopting in the present invention does not preferably pass through hydrotreated paraffin oil, contains two keys in this paraffin oil, is easy to and unsaturated polar monomer polymerization.
Unsaturated polar monomer described in the present invention contains two keys or triple bond, is easy to polymerization, and the existence of polar group makes its and paraffin oil suitably produce gathering, while being applied to battery diaphragm manufacture, can obtain equally distributed macropore.In embodiment of the present invention, preferred unsaturated polar monomer is that one or more in methyl methacrylate, butyl methacrylate, vinyl cyanide, glycidyl methacrylate, phenyl maleimide are with arbitrarily than mixing.
Radical initiator of the present invention is that one or more in organo-peroxide class or azo compound are with arbitrarily than mixing.
Preferably, described organo-peroxide type free base initiator comprises 1,1-bis-(tert-butyl peroxy base)-3,3,5-trimethyl-cyclohexane, ethyl ketone, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis-(tert-butyl peroxy base) hexane, 4,4-bis-(tert-butyl peroxy base) n-butyl pentanoate; Described azo compound comprises 1,1 '-azo two (hexanaphthene-1-nitrile), 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2-acetyl oxygen butane), 2-phenylazo-4-methoxyl group-2,4-methyl pentane nitrile.
A kind of method of preparing above-mentioned modification pore-creating agent, it is characterized in that: after paraffin oil, unsaturated polar monomer, radical initiator three are mixed, join in reactor, at the uniform velocity stir, be heated to initiator working temperature reaction 1-2 hour, cooling discharging.
Modification pore-creating agent of the present invention is applied to prepare in lithium ion battery separator.
, it is to be prepared from by polyolefin resin and modification pore-creating agent claimed in claim 1, wherein the consumption of polyolefine and modification pore-creating agent is respectively in weight part: polyolefin resin 60-80 part, modification pore-creating agent 20-40 part.
In such scheme, described polyolefine is a kind of in polyvinyl resin, acrylic resin.
The preparation method of lithium ion battery separator of the present invention, it comprises the following steps:
1) melting mixing: in proportion that polyolefin resin and modification pore-creating agent melting mixing at 100-280 ℃ of temperature is even;
2) extrude: the material of step 1) is melt extruded, and the flat film of extruding is cooling with cooling roller;
3) stretch: above-mentioned cooling flat film through successively through vertically drawing, horizontal successive processes of drawing, and after heat setting type.
In above-mentioned preparation method, step 2) cooling temperature is-20-100 ℃ that be 0.1-5 minute cooling time; In step 3), draft temperature is-20-220 ℃, and heat setting temperature is 0-220 ℃, and heat-setting time is 0.1-20 minute.
Compared to existing technology, beneficial effect of the present invention is: the present invention improves the performance of lithium ion battery separator from pore-creating agent, in order to prepare powerful lithium cell.Modification pore-creating agent of the present invention is by method appropriate grafting polar group on paraffin oil of chemical graft, on the one hand, changed the polarity of paraffin oil, at high temperature, the equally distributed polarity paraffin oil of part and PE consistency are poor, easily suitably assemble, can be for the preparation of larger hole battery diaphragm, and at a lower temperature, the paraffin oil after modification is easy to occur separated with polyolefine, thereby the barrier film of preparing has higher ventilation property, be applicable to making high-power lithium ion battery; On the other hand, when preparing lithium ion battery separator with modification pore-creating agent of the present invention, residual a small amount of modified paraffin oil in barrier film, due to the grafting of its modified paraffin oil polar monomer, in barrier film hole, be easy to infiltrate and Electolyte-absorptive, be conducive to improve the capacity of battery, be applicable to making high-capacity battery.Lithium ion battery separator of the present invention has added modification pore-creating agent of the present invention in preparation process, thereby has the ability of good ventilation property, wetting property and Electolyte-absorptive.
Below in conjunction with concrete embodiment, the present invention is described in further detail.
Embodiment
Embodiment 1
A kind of modification pore-creating agent, by paraffin oil, methyl methacrylate, 2, after 2 '-Diisopropyl azodicarboxylate three mixes, join in reactor, at the uniform velocity stir, be heated to initiator working temperature reaction 1-2 hour, cooling discharging forms, wherein the consumption of paraffin oil, methyl methacrylate, 2,2 '-Diisopropyl azodicarboxylate is respectively with listed as parts by weight: 100 parts, 0.5 part, 0.5 part, obtain modification pore-creating agent called after A.
Embodiment 2
A kind of modification pore-creating agent, after paraffin oil, vinyl cyanide, di-t-butyl peroxide three are mixed, join in reactor, at the uniform velocity stir, be heated to initiator working temperature reaction 1-2 hour, cooling discharging forms, and wherein the consumption of paraffin oil, vinyl cyanide, di-t-butyl peroxide is respectively with listed as parts by weight: 100 parts, 1 part, 0.5 part, obtain modification pore-creating agent called after B.
Embodiment 3
A kind of modification pore-creating agent, after paraffin oil, phenyl maleimide, di-t-butyl peroxide three are mixed, join in reactor, at the uniform velocity stir, be heated to initiator working temperature reaction 1-2 hour, cooling discharging forms, and wherein the consumption of paraffin oil, phenyl maleimide, di-t-butyl peroxide is respectively with listed as parts by weight: 100 parts, 2 parts, 1 part, obtain modification pore-creating agent called after C.
Application Example
In this embodiment by above-described embodiment 1-3 for the preparation of lithium ion battery separator, preparation method is:
1) melting mixing: in proportion that polyolefin resin and modification pore-creating agent melting mixing is even;
2) extrude: the material of step 1) is melt extruded, and the flat film of extruding is cooling with cooling roller;
3) stretch: above-mentioned cooling flat film through successively through vertically drawing, horizontal successive processes of drawing, and after heat setting type;
Concrete proportioning and reaction conditions are in Table 1.
Table 1
Table 2 is Performance Detection of above-mentioned Application Example and comparative example.
Table 2
From upper table data, can see, the barrier film that modified paraffin oil makes, tensile strength and 105 ℃ of percent thermal shrinkages change little, maximum discharge-rate is brought up to 6C by 5C, 1500mAh cell container improves, these show that the power of battery and the capacity of the barrier film that modified paraffin oil makes are improved under the constant prerequisite of barrier film fundamental property.
Above-mentioned embodiment is only the preferred embodiment of the present invention; can not limit the scope of protection of the invention with this, the variation of any unsubstantiality that those skilled in the art does on basis of the present invention and replacement all belong to the present invention's scope required for protection.
Claims (10)
1. a modification pore-creating agent, is characterized in that: it is to be formed by radical polymerization by paraffin oil and polar monomer, and in reaction, wherein the mass ratio of paraffin oil, unsaturated polar monomer and radical initiator is 100:(0.5-2): (0.5-1).
2. modification pore-creating agent according to claim 1, is characterized in that: described unsaturated polar monomer is that one or more in methyl methacrylate, butyl methacrylate, vinyl cyanide, glycidyl methacrylate, phenyl maleimide are with arbitrarily than mixing.
3. modification pore-creating agent according to claim 1, is characterized in that: described radical initiator is that one or more in organo-peroxide class or azo compound are with arbitrarily than mixing.
4. modification pore-creating agent according to claim 3, it is characterized in that: described organo-peroxide type free base initiator comprises 1,1-bis-(tert-butyl peroxy base)-3,3,5-trimethyl-cyclohexane, ethyl ketone, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis-(tert-butyl peroxy base) hexane, 4,4-bis-(tert-butyl peroxy base) n-butyl pentanoate; Described azo compound comprises 1,1 '-azo two (hexanaphthene-1-nitrile), 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2-acetyl oxygen butane), 2-phenylazo-4-methoxyl group-2,4-methyl pentane nitrile.
5. a method of preparing the modification pore-creating agent as described in claim 1-4 any one, it is characterized in that: after paraffin oil, unsaturated polar monomer, radical initiator three are mixed, join in reactor, at the uniform velocity stir, be heated to initiator working temperature reaction 1-2 hour, cooling discharging.
6. the application of the modification pore-creating agent as described in claim 1-4 any one in preparing lithium ion battery separator.
7. a lithium ion battery separator, it is characterized in that: it is to be prepared from by polyolefin resin and modification pore-creating agent claimed in claim 1, wherein the consumption of polyolefine and modification pore-creating agent is respectively in weight part: polyolefin resin 60-80 part, modification pore-creating agent 20-40 part.
8. lithium ion battery separator according to claim 7, is characterized in that: described polyolefine is a kind of in polyvinyl resin, acrylic resin.
9. a preparation method for lithium ion battery separator as claimed in claim 7, is characterized in that it comprises the following steps:
1) melting mixing: in proportion that polyolefin resin and modification pore-creating agent melting mixing at 100-280 ℃ of temperature is even;
2) extrude: the material of step 1) is melt extruded, and the flat film of extruding is cooling with cooling roller;
3) stretch: above-mentioned cooling flat film through successively through vertically drawing, horizontal successive processes of drawing, and after heat setting type.
10. preparation method according to claim 1, is characterized in that: step 2) in, cooling temperature is-20-100 ℃ that be 0.1-5 minute cooling time; In step 3), draft temperature is-20-220 ℃, and heat setting temperature is 0-220 ℃, and heat-setting time is 0.1-20 minute.
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| CN201310432963.4A CN103524778B (en) | 2013-09-22 | 2013-09-22 | A kind of modification pore-creating agent and preparation method thereof and its application in lithium ion battery separator |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104183807A (en) * | 2014-08-21 | 2014-12-03 | 上海市凌桥环保设备厂有限公司 | Method for modifying PE film and PTFE film composite membrane for lithium ion battery |
| CN104201313A (en) * | 2014-08-21 | 2014-12-10 | 上海市凌桥环保设备厂有限公司 | Method for modifying membrane compounded by polypropylene (PP) membrane and polytetrafluoroethylene (PTFE) membrane and applied to lithium ion battery |
| CN107298733A (en) * | 2017-07-20 | 2017-10-27 | 东莞南玻太阳能玻璃有限公司 | A kind of anti-reflection anti-reflection coating liquid template and its preparation method and application |
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| CN103268924A (en) * | 2013-05-10 | 2013-08-28 | 佛山市金辉高科光电材料有限公司 | Polyolefin micro porous membrane and preparation method thereof |
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| CN103268924A (en) * | 2013-05-10 | 2013-08-28 | 佛山市金辉高科光电材料有限公司 | Polyolefin micro porous membrane and preparation method thereof |
| CN103301818A (en) * | 2013-07-03 | 2013-09-18 | 苏州天立蓝环保科技有限公司 | Method for preparing fibrous macromolecule adsorption material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104183807A (en) * | 2014-08-21 | 2014-12-03 | 上海市凌桥环保设备厂有限公司 | Method for modifying PE film and PTFE film composite membrane for lithium ion battery |
| CN104201313A (en) * | 2014-08-21 | 2014-12-10 | 上海市凌桥环保设备厂有限公司 | Method for modifying membrane compounded by polypropylene (PP) membrane and polytetrafluoroethylene (PTFE) membrane and applied to lithium ion battery |
| CN104183807B (en) * | 2014-08-21 | 2016-09-28 | 上海市凌桥环保设备厂有限公司 | The lithium ion battery method of PE film with the composite diaphragm modification of PTFE film |
| CN107298733A (en) * | 2017-07-20 | 2017-10-27 | 东莞南玻太阳能玻璃有限公司 | A kind of anti-reflection anti-reflection coating liquid template and its preparation method and application |
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