CN101340010A - Preparation of gel polymer electrolyte - Google Patents
Preparation of gel polymer electrolyte Download PDFInfo
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- CN101340010A CN101340010A CNA2008100488151A CN200810048815A CN101340010A CN 101340010 A CN101340010 A CN 101340010A CN A2008100488151 A CNA2008100488151 A CN A2008100488151A CN 200810048815 A CN200810048815 A CN 200810048815A CN 101340010 A CN101340010 A CN 101340010A
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Abstract
The invention relates to a preparation method of a gel polymer electrolyte. The preparation method of the gel polymer electrolyte is characterized by comprising the following steps: (1) A reaction vessel is added with deionized water, sodium laurylsulfate and methyl metharcrylate, and is filled with nitrogen gas for mixing and emulsification for 20-40 minutes, thus an emulsified mixture is obtained; (2) potassium persulphate of an evocating agent is added to react for 3-5 hours to obtain polymer emulsion; (3) acrylonitrile and styrene are slowly dripped into the polymer emulsion for heat preservation and reaction for 5-8 hours; the mixture obtained is demulsified, washed, filtered and dried to obtain white polymer solid; (4) the white polymer solid is mixed with N-N dimethyl formamide and nanometer SiO2, and is stirred until the white polymer solid is completely dissolved, so as to obtain viscous fluid; (5) the viscous fluid is coated on glass by rolling and is added with the deionized water for phase transformation for 30-60min, the mixture obtained is washed with water, and dried to obtain a polymer membrane, then the polymer membrane is soaked into an organic electrolyte, therefore, the gel polymer electrolyte is obtained. The preparation method of the gel polymer electrolyte is characterized by high conductivity and good mechanical performance.
Description
Technical field
The present invention relates to a kind of method for preparing gel polymer electrolyte.
Background technology
Polymer Li-ion battery has light weight, energy density height, good cycle, no leakage, encapsulates advantages such as simple, therefore receives much concern.The polymer dielectric that is widely studied at present mainly contains systems such as PAN, PEO, PMMA, PVC, PVDF, this class research also is in laboratory stage at present mostly, still have certain gap apart from coml large-scale production and application, the subject matter that these systems face at present is that high ionic conductivity and favorable mechanical performance can not be met simultaneously.For mechanical property and the conductive capability that improves gelatin polymer, adopt at present usually methods such as copolymerization, grafting, crosslinked, blend, adding inorganic filler.Copolymerization is the effective way that reduces the polymer crystallization degree, and might obtain the unexistent property of homopolymers; Grafting is the polymer modification method of using always, can prevent the crystallization of polymer, helps the raising of conductivity; Crosslinked is the effective means that suppresses crystallization, and can improve mechanical strength and thermal stability greatly after crosslinked; Blend also is the effective means that suppresses polymer crystallization, but the blend effect that will obtain must have good compatibility between the polymer; The purpose that adds inorganic filler is to reduce the crystallizing power of polymer, improves its conductivity, improves the mechanical performance of system.
China is liquid lithium ionic cell big producing country now, and also very backward aspect the production technology of polymer Li-ion battery.Main cause is to lack the polymeric material technology of preparing with independent intellectual property right, can not produce high-quality polymer Li-ion battery.The preparation of polymer dielectric has become the bottleneck of China's lithium ion battery being pushed to the international market.
Summary of the invention
The object of the present invention is to provide the method for preparing gel polymer electrolyte of a kind of conductivity height, good mechanical property.
To achieve these goals, technical scheme of the present invention is: a kind of method for preparing gel polymer electrolyte is characterized in that it comprises the steps:
1) proportioning by deionized water, emulsifier sodium lauryl sulfate, methyl methacrylate is 60～70g: 1.0～2.0g: 7.0～7.5g, chooses deionized water, lauryl sodium sulfate and methyl methacrylate; In reaction vessel, add deionized water, lauryl sodium sulfate and methyl methacrylate, and feed nitrogen, fully stirring, emulsification are 20～40 minutes; Get emulsion;
2) reaction vessel that will fill emulsion is heated to 60～75 ℃ of reaction temperatures in thermostat water bath, and adding initiator potassium persulfate reaction 3～5 hours, the addition of potassium peroxydisulfate is 0.3～0.5% of deionized water, lauryl sodium sulfate and a methyl methacrylate gross mass; Get polymer emulsion;
3) be that 7.0～7.5g: 7.5～8.5g: 4.5～5.0g chooses acrylonitrile and styrene by methyl methacrylate, acrylonitrile, cinnamic proportioning; Acrylonitrile and styrene slowly are added drop-wise in the polymer emulsion that the step reaction obtains, dripped off in 14～16 minutes, then 60～75 ℃ of following insulation reaction 5～8 hours; The vacuum drying chamber of putting into 50～70 ℃ behind the breakdown of emulsion washing and filtering dried by the fire 24～30 hours, obtained the white polymer solid;
4) mass ratio by white polymer solid and N-N dimethyl formamide is 1: 9～10, nanometer SiO
2Quality be 1～10% of white polymer solid masses, choose N-N dimethyl formamide and nanometer SiO
2With white polymer solid and N-N dimethyl formamide and the nanometer SiO for preparing
2Mix, be stirred to dissolving fully after, obtain viscous fluid;
5) arrive the viscous fluid roller coating that obtains on glass, put into deionized water then, inversion of phases 30～60 minutes, and after washing with flow deionized water, the vacuum drying chamber of putting into 50～70 ℃ again dried by the fire 24～30 hours, obtain polymer film, this polymer film is immersed in the organic electrolyte, obtain gel polymer electrolyte.
The present invention is in conjunction with crosslinking copolymerization and add the Surface Modification Of Inorganic Fillers effect, adopt emulsion polymerization to prepare the matrix that the PAN interpenetrating polymer networks (IPN) that contains other monomers is made polymer dielectric, adopt phase inversion to prepare gel polymer electrolyte on this basis, to reach no liquid electrolyte, the technical characterstic of higher chemical property is arranged simultaneously again.
The invention has the beneficial effects as follows: by the gel polymer electrolyte (LIPN) of core-shell emulsion polymerization method preparation, also can claim porous polymer electrolyte, have the premium properties of the various polymer that constitute LIPN concurrently, the polymer phase ratio that obtains with general copolymerization process shows excellent performance at aspects such as intermiscibility, glass transition temperature and the film forming of polymer, rheological characteristic, conductivity.The electrolyte of preparing by phase inversion helps simplifying equipment technology, the design novel battery profile of battery and reduces cost, can guarantee the high conductivity of polymer dielectric and stronger mechanical performance (being conductivity height, the good mechanical property of gel polymer electrolyte of the present invention) preferably simultaneously, be satisfied with the application of polymer Li-ion battery.Preparation method of the present invention, its mild condition is controlled, product yield height, favorable reproducibility, industrialization production feasibility height; Therefore higher actual application ability and market prospects are arranged.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with example, but content of the present invention not only is confined to the following examples.
Embodiment 1:
A kind of method for preparing gel polymer electrolyte, it comprises the steps:
1) proportioning by deionized water, emulsifier sodium lauryl sulfate (SDS), methyl methacrylate (after refining) is 60g: 1.0g: 7.0g, chooses deionized water, lauryl sodium sulfate and methyl methacrylate; (the four-hole round-bottomed flask of reflux condensing tube, mechanical agitator, nitrogen ingress pipe and separatory funnel is housed) in reaction vessel, adds deionized water, lauryl sodium sulfate and methylacrylic acid methyl esters, and feed nitrogen, fully stirring, emulsification are 20 minutes; Get emulsion;
2) reaction vessel that will fill emulsion is heated to 60 ℃ of reaction temperatures in thermostat water bath, and adding initiator potassium persulfate reaction 3 hours, the addition of potassium peroxydisulfate is 0.3% of deionized water, lauryl sodium sulfate and a methyl methacrylate gross mass; Get polymer emulsion;
3) be that 7.0g: 7.5g: 4.5g chooses acrylonitrile and styrene by methyl methacrylate, acrylonitrile, cinnamic proportioning; Acrylonitrile (after refining) and styrene (after refining) slowly are added drop-wise to go on foot and react in the polymer emulsion that obtains, dripped off in 14 minutes, then 60 ℃ of following insulation reaction 5 hours; The vacuum drying chamber of putting into 50 ℃ behind the breakdown of emulsion washing and filtering dried by the fire 24 hours, obtained the white polymer solid;
4) mass ratio by white polymer solid and N-N dimethyl formamide is 1: 9, nanometer SiO
2Quality be 1% of white polymer solid masses, choose N-N dimethyl formamide and nanometer SiO
2With white polymer solid and N-N dimethyl formamide and the nanometer SiO for preparing
2Mix, be stirred to dissolving fully after, obtain viscous fluid;
5) arrive the viscous fluid roller coating that obtains on glass, put into deionized water then, inversion of phases 30 minutes, and after washing with flow deionized water, the vacuum drying chamber of putting into 50 ℃ again dried by the fire 24 hours, obtained polymer film, and this polymer film is immersed in organic electrolyte, and (the production model LB315 of Hua Rong company of Zhangjiagang Cathay or Shantou City, Guangdong golden light High Seience Technology Co., Ltd. produce, model L14) in, obtains gel polymer electrolyte.
Embodiment 2:
A kind of method for preparing gel polymer electrolyte, it comprises the steps:
1) proportioning by deionized water, emulsifier sodium lauryl sulfate (SDS), methyl methacrylate (after refining) is 65g: 1.5g: 7.2g, chooses deionized water, lauryl sodium sulfate and methyl methacrylate; (the four-hole round-bottomed flask of reflux condensing tube, mechanical agitator, nitrogen ingress pipe and separatory funnel is housed) in reaction vessel, adds deionized water, lauryl sodium sulfate and methyl methacrylate, and feed nitrogen, fully stirring, emulsification are 30 minutes; Get emulsion;
2) reaction vessel that will fill emulsion is heated to 68 ℃ of reaction temperatures in thermostat water bath, and adding initiator potassium persulfate reaction 4 hours, the addition of potassium peroxydisulfate is 0.4% of deionized water, lauryl sodium sulfate and a methyl methacrylate gross mass; Get polymer emulsion;
3) be that 7.2g: 8.0g: 4.8g chooses acrylonitrile and styrene by methyl methacrylate, acrylonitrile, cinnamic proportioning; Acrylonitrile (after refining) and styrene (after refining) slowly are added drop-wise to go on foot and react in the polymer emulsion that obtains, dripped off in 15 minutes, then 68 ℃ of following insulation reaction 6 hours; The vacuum drying chamber of putting into 60 ℃ behind the breakdown of emulsion washing and filtering dried by the fire 26 hours, obtained the white polymer solid;
4) mass ratio by white polymer solid and N-N dimethyl formamide is 1: 9.5, nanometer SiO
2Quality be 5% of white polymer solid masses, choose N-N dimethyl formamide, nanometer SiO
2With white polymer solid and N-N dimethyl formamide and the nanometer SiO for preparing
2Mix, be stirred to dissolving fully after, obtain viscous fluid;
5) arrive the viscous fluid roller coating that obtains on glass, put into deionized water then, inversion of phases 40 minutes, and after washing with flow deionized water, put into 60 ℃ vacuum drying chamber baking 28 hours again, obtain polymer film, this polymer film is immersed in organic electrolyte, and (Hua Rong company of Zhangjiagang Cathay produces, model LB315 or Shantou City, Guangdong golden light High Seience Technology Co., Ltd. produce, model L14) in, gel polymer electrolyte obtained.
Embodiment 3:
A kind of method for preparing gel polymer electrolyte, it comprises the steps:
1) proportioning by deionized water, emulsifier sodium lauryl sulfate (SDS), methyl methacrylate is 70g: 2.0g: 7.5g, chooses deionized water, lauryl sodium sulfate and methyl methacrylate; (the four-hole round-bottomed flask of reflux condensing tube, mechanical agitator, nitrogen ingress pipe and separatory funnel is housed) in reaction vessel, adds deionized water, lauryl sodium sulfate and methyl methacrylate, and feed nitrogen, fully stirring, emulsification are 40 minutes; Get emulsion;
2) reaction vessel that will fill emulsion is heated to 75 ℃ of reaction temperatures in thermostat water bath, and adding initiator potassium persulfate reaction 5 hours, the addition of potassium peroxydisulfate is 0.5% of deionized water, lauryl sodium sulfate and a methyl methacrylate gross mass; Get polymer emulsion;
3) be that 7.5g: 8.5g: 5.0g chooses acrylonitrile and styrene by methyl methacrylate, acrylonitrile, cinnamic proportioning; Acrylonitrile and styrene slowly are added drop-wise in the polymer emulsion that the step reaction obtains, dripped off in 16 minutes, then 75 ℃ of following insulation reaction 8 hours; The vacuum drying chamber of putting into 70 ℃ behind the breakdown of emulsion washing and filtering dried by the fire 30 hours, obtained the white polymer solid;
4) mass ratio by white polymer solid and N-N dimethyl formamide is 1: 10, nanometer SiO
2Quality be 10% of white polymer solid masses, choose N-N dimethyl formamide and nanometer SiO
2With white polymer solid and N-N dimethyl formamide and the nanometer SiO for preparing
2Mix, be stirred to dissolving fully after, obtain viscous fluid;
5) arrive the viscous fluid roller coating that obtains on glass, put into deionized water then, inversion of phases 60 minutes, and after washing with flow deionized water, put into 70 ℃ vacuum drying chamber baking 30 hours again, obtain polymer film, this polymer film is immersed in organic electrolyte (Hua Rong company of Zhangjiagang Cathay production model, LB315 or Shantou City, Guangdong golden light High Seience Technology Co., Ltd. produce, model L14) in, gel polymer electrolyte obtained.
Claims (1)
1. a method for preparing gel polymer electrolyte is characterized in that it comprises the steps:
1) proportioning by deionized water, emulsifier sodium lauryl sulfate, methyl methacrylate is 60～70g: 1.0～2.0g: 7.0～7.5g, chooses deionized water, lauryl sodium sulfate and methyl methacrylate; In reaction vessel, add deionized water, lauryl sodium sulfate and methyl methacrylate, and feed nitrogen, fully stirring, emulsification are 20～40 minutes; Get emulsion;
2) reaction vessel that will fill emulsion is heated to 60～75 ℃ of reaction temperatures in thermostat water bath, and adding initiator potassium persulfate reaction 3～5 hours, the addition of potassium peroxydisulfate is 0.3～0.5% of deionized water, lauryl sodium sulfate and a methyl methacrylate gross mass; Get polymer emulsion;
3) be that 7.0～7.5g: 7.5～8.5g: 4.5～5.0g chooses acrylonitrile and styrene by methyl methacrylate, acrylonitrile, cinnamic proportioning; Acrylonitrile and styrene slowly are added drop-wise in the polymer emulsion that the step reaction obtains, dripped off in 14～16 minutes, then 60～75 ℃ of following insulation reaction 5～8 hours; The vacuum drying chamber of putting into 50～70 ℃ behind the breakdown of emulsion washing and filtering dried by the fire 24～30 hours, obtained the white polymer solid;
4) mass ratio by white polymer solid and N-N dimethyl formamide is 1: 9～10, nanometer SiO
2Quality be 1～10% of white polymer solid masses, choose N-N dimethyl formamide and nanometer SiO
2With white polymer solid and N-N dimethyl formamide and the nanometer SiO for preparing
2Mix, be stirred to dissolving fully after, obtain viscous fluid;
5) arrive the viscous fluid roller coating that obtains on glass, put into deionized water then, inversion of phases 30～60 minutes, and after washing with flow deionized water, the vacuum drying chamber of putting into 50～70 ℃ again dried by the fire 24～30 hours, obtain polymer film, this polymer film is immersed in the organic electrolyte, obtain gel polymer electrolyte.
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| CNB2008100488151A CN100568609C (en) | 2008-08-14 | 2008-08-14 | A kind of method for preparing gel polymer electrolyte |
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| CNB2008100488151A CN100568609C (en) | 2008-08-14 | 2008-08-14 | A kind of method for preparing gel polymer electrolyte |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101841013A (en) * | 2010-02-11 | 2010-09-22 | 华南师范大学 | Polymer isolating membrane and lithium ion battery applying same |
| CN102694203A (en) * | 2012-05-29 | 2012-09-26 | 深圳华粤宝电池有限公司 | Preparation method of gel polymer electrolyte |
| CN103840207A (en) * | 2014-03-12 | 2014-06-04 | 中国海诚工程科技股份有限公司 | High temperature resistant lithium ion battery gel polymer electrolyte and preparation method thereof |
| CN104558390A (en) * | 2013-10-12 | 2015-04-29 | 深圳华粤宝电池有限公司 | Polymer for gel polymer electrolyte, preparation method of polymer, gel polymer electrolyte and preparation method of gel polymer electrolyte |
-
2008
- 2008-08-14 CN CNB2008100488151A patent/CN100568609C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101841013A (en) * | 2010-02-11 | 2010-09-22 | 华南师范大学 | Polymer isolating membrane and lithium ion battery applying same |
| CN101841013B (en) * | 2010-02-11 | 2012-07-04 | 华南师范大学 | Polymer isolating membrane and lithium ion battery applying same |
| CN102694203A (en) * | 2012-05-29 | 2012-09-26 | 深圳华粤宝电池有限公司 | Preparation method of gel polymer electrolyte |
| CN102694203B (en) * | 2012-05-29 | 2014-11-05 | 深圳华粤宝电池有限公司 | Preparation method of gel polymer electrolyte |
| CN104558390A (en) * | 2013-10-12 | 2015-04-29 | 深圳华粤宝电池有限公司 | Polymer for gel polymer electrolyte, preparation method of polymer, gel polymer electrolyte and preparation method of gel polymer electrolyte |
| CN104558390B (en) * | 2013-10-12 | 2017-09-15 | 深圳华粤宝电池有限公司 | Gel polymer electrolyte polymer and preparation method thereof and gel polymer electrolyte and preparation method thereof |
| CN103840207A (en) * | 2014-03-12 | 2014-06-04 | 中国海诚工程科技股份有限公司 | High temperature resistant lithium ion battery gel polymer electrolyte and preparation method thereof |
| CN103840207B (en) * | 2014-03-12 | 2016-09-14 | 中国海诚工程科技股份有限公司 | A kind of resistant to elevated temperatures lithium ion battery gel polymer electrolyte and preparation method thereof |
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| CN100568609C (en) | 2009-12-09 |
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Granted publication date: 20091209 Termination date: 20110814 |