CN100560648C - The single stage method initiated polymerization prepares the method for nano silicon dioxide/polymethyl methacrylate gel polymer dielectric - Google Patents
The single stage method initiated polymerization prepares the method for nano silicon dioxide/polymethyl methacrylate gel polymer dielectric Download PDFInfo
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- CN100560648C CN100560648C CNB2006100431258A CN200610043125A CN100560648C CN 100560648 C CN100560648 C CN 100560648C CN B2006100431258 A CNB2006100431258 A CN B2006100431258A CN 200610043125 A CN200610043125 A CN 200610043125A CN 100560648 C CN100560648 C CN 100560648C
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- silicon dioxide
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- polymethyl methacrylate
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Abstract
The present invention relates to the method that a kind of single stage method initiated polymerization prepares the nano silicon dioxide/polymethyl methacrylate gel polymer dielectric, its special character is: be monomer with the methyl methacrylate, nano silicon is a modified particle, (electrolyte solution of 1mol/L is as solvent for the lithium perchlorate/propylene carbonate for preparing, directly mix, heating in water bath to 80 ℃ carries out solution polymerization, react after 2.5 hours, reaction gel liquid is prolonged the stream film forming on sheet glass, can obtain the gel-type electrolytic thin-membrane at 60 ℃ of vacuum-drying 8h.Beneficial effect: present method technology is simple, and is feasible, adopts the solvent of electrolytic solution as polyreaction, can take away a large amount of heat of polymerizations that Raolical polymerizable produces, and directly prepares coagulant liquid; The gel polymer electrolyte of preparation has gratifying ionic conductivity, and has good dimensional stability and chemistry, electrochemical stability.
Description
Technical field
The present invention relates to the method that a kind of single stage method initiated polymerization prepares the nano silicon dioxide/polymethyl methacrylate gel polymer dielectric, belong to the interdisciplinary field of electricity and materialogy.
Background technology
Adding nanoparticle in recent years is to improve the simplest method of gel-type ionogen mechanical property, discover, in gel electrolyte, add ceramics powder or other mineral filler, not only can make ionogen have gratifying ionic conductivity, chemical stability and electrochemical stability, and to have the favorable mechanical performance be dimensional space stability.Nanoparticle commonly used has clay, SiO
2, zeolite, Al
2O
3Deng.
One carbonyl side group is arranged in the unit of polymethylmethacrylate (PMMA), very strong effect is arranged, therefore can contain a large amount of liquid electrolytes, have good consistency with oxygen in the carbonates softening agent; And PMMA series gel electrolyte has interface stability preferably to lithium electrode, and is low with the interface impedance of metal lithium electrode.Add the PMMA abundant raw material, preparation is simple, low price, thus cause the extensive interest of investigator to PMMA base gel electrolyte.
Bibliographical information SiO is arranged both at home and abroad
2Nanoparticle and PMMA adopt blending method to prepare gel polymer electrolyte, common blending method dispersing nanometer particle, can make system viscosity cause the nanoparticle degree of scatter lower more greatly, also there is the investigator to adopt other secondary solvents of interpolation to reduce system viscosity, but also need remove behind the thorough mixing, thereby cause problems such as complex process and environmental pollution more than solvent.
Summary of the invention
The technical problem that solves
For fear of the deficiencies in the prior art part, the present invention proposes the method that a kind of single stage method initiated polymerization prepares the nano silicon dioxide/polymethyl methacrylate gel polymer dielectric, synthetic from polymeric matrix adopts single stage method to prepare the nano silicon dioxide/polymethyl methacrylate (SiO with good ionic conductivity and dimensional stability
2/ PMMA) gel polymer electrolyte.
Technical scheme
Silicon dioxide/polymethyl methacrylate (SiO provided by the present invention
2/ PMMA) gel polymer electrolyte is with nano-silicon dioxide particle (SiO
2) as additive, methyl methacrylate (MMA) monomer, Diisopropyl azodicarboxylate (AIBN) is an initiator, lithium perchlorate (LiClO
4) as lithium salts, propylene carbonate (PC) directly mixes each component as the solvent of polymerization system, adopts free radical to cause, the mode of solution polymerization, single stage method make the silicon dioxide/polymethyl methacrylate (SiO of homogeneous
2/ PMMA) gel electrolyte system.
Technical characterictic of the present invention is:
A) with lithium perchlorate LiCiO
4Be dissolved among the propylene carbonate PC, be made into the organic electrolyte solution that concentration is 0.9-1.3mol/L;
B) with nano-silicon dioxide particle as additive, monomers methyl methacrylate and Diisopropyl azodicarboxylate are after initiator mixes, and add the organic electrolyte solution for preparing as solvent;
C), react after 2.5 hours reaction gel liquid is prolonged the stream film forming on sheet glass, and the aftertreatment through 4-12 hour promptly obtains the nano silicon dioxide/polymethyl methacrylate gel polymer dielectric under 50-70 ℃ 60-80 ℃ of stirred in water bath.
Above-mentioned each component is mixed by following proportioning:
Methyl methacrylate MMA:20-30g
Silicon-dioxide: 2～8g
Organic electrolyte solution: 20-50g
Diisopropyl azodicarboxylate: 0.04-0.1g.
Beneficial effect
The present invention adopts single stage method with SiO
2Nanoparticle mixes with monomer and adds the initiator polymerization reaction take place, in polymerization process, and SiO
2The intensive hydrogen bond action can take place with organic softening agent propylene carbonate PC in the unsaturated double-bond and the silicon hydroxyl on surface, and each component is held fully mutually, thereby forms homogeneous phase gel type ionogen; Big specific surface area can make it absorb a large amount of liquid electrolytes simultaneously, improves the stability of gel electrolyte; The method of this solution polymerization can also be prepared the gel polymer electrolyte of different performance as required by changing the proportioning and the polymerization technique of each component in addition.
Adopt single stage method to prepare silicon dioxide/polymethyl methacrylate (SiO
2/ PMMA) gel polymer electrolyte, technology is simple, and is feasible, adopts the solvent of electrolytic solution as polyreaction, can take away a large amount of heat of polymerizations that Raolical polymerizable produces, and directly prepares coagulant liquid; The gel polymer electrolyte of preparation has gratifying ionic conductivity, and has good dimensional stability and chemistry, electrochemical stability.
Description of drawings
Fig. 1: the single stage method initiated polymerization prepares the method block diagram of nano silicon dioxide/polymethyl methacrylate gel polymer dielectric
Embodiment
Now in conjunction with the accompanying drawings the present invention is further described:
Silicon-dioxide is the nano silicon of buying, methyl methacrylate (MMA), Diisopropyl azodicarboxylate (AIBN), softening agent propylene carbonate (PC), lithium perchlorate (LiClO
4) be commercial grade reagent.
Embodiment 1:
2.5g lithium perchlorate salt LiCiO
4Be dissolved among the 27.5g propylene carbonate PC and be made into 1ML
-1Organic solution 30g; The 20g methyl methacrylate, 0.05g Diisopropyl azodicarboxylate, 1.5g nanometer SiO2, the 30g organic electrolyte, the thorough mixing stirring reaction is 2.5 hours in 80 water-baths, to obtain to such an extent that colloidal state electrolytic solution pours into film, drying is 8 hours under 60 ℃ of vacuum, promptly gets silicon dioxide/polymethyl methacrylate gel polymer ionogen (1phr-SiO
2/ PMMA).Under concurrent this proportioning now, the silicon dioxide/polymethyl methacrylate (SiO that makes
2/ PMMA) gel polymer electrolyte has good spatial stability and mechanical mechanics property, and satisfied well as the requirement of lithium ion battery electrolyte to ionic conductivity.
Embodiment 2:
2.5g lithium perchlorate salt LiCiO
4Be dissolved among the 27.5g propylene carbonate PC and be made into 1ML
-1Organic solution 30g; The 20g methyl methacrylate, 0.05g dibenzoyl peroxide (BPO), 3g nanometer SiO2, the 30g organic electrolyte, the thorough mixing stirring reaction is 2.5 hours in 80 water-baths, to obtain to such an extent that colloidal state electrolytic solution pours into film, drying is 8 hours under 60 ℃ of vacuum, promptly gets silicon dioxide/polymethyl methacrylate gel polymer ionogen (2phr-SiO
2/ PMMA).Under concurrent this proportioning now, the silicon dioxide/polymethyl methacrylate (SiO that makes
2/ PMMA) gel polymer electrolyte has good spatial stability and mechanical mechanics property, and satisfied well as the requirement of lithium ion battery electrolyte to ionic conductivity.
Embodiment 3:
2.5g lithium perchlorate salt LiCiO
4Be dissolved among the 27.5g propylene carbonate PC and be made into 1ML
-1Organic solution 30g; The 20g methyl methacrylate, 0.05g Diisopropyl azodicarboxylate, 5g nanometer SiO2, the 30g organic electrolyte, the thorough mixing stirring reaction is 2.5 hours in 80 water-baths, to obtain to such an extent that colloidal state electrolytic solution pours into film, drying is 8 hours under 60 ℃ of vacuum, promptly gets silicon dioxide/polymethyl methacrylate gel polymer ionogen (5phr-SiO
2/ PMMA).Under concurrent this proportioning now, the silicon dioxide/polymethyl methacrylate (SiO that makes
2/ PMMA) gel polymer electrolyte has good spatial stability and mechanical mechanics property, and satisfied well as the requirement of lithium ion battery electrolyte to ionic conductivity.
The specific performance of the gel electrolyte system that three kinds of embodiments obtain is as follows:
※ all records under 25 ℃
Claims (1)
1. a single stage method initiated polymerization prepares the method for nano silicon dioxide/polymethyl methacrylate gel polymer dielectric, it is characterized in that:
A) with lithium perchlorate LiClO
4Be dissolved among the propylene carbonate PC, be made into the organic electrolyte solution that concentration is 0.9-1.3mol/L;
B) with nano-silicon dioxide particle as additive, monomers methyl methacrylate and Diisopropyl azodicarboxylate are after initiator mixes, and add the organic electrolyte solution for preparing as solvent;
C), react after 2.5 hours reaction gel liquid is prolonged the stream film forming on sheet glass, and the aftertreatment through 4-12 hour promptly obtains the nano silicon dioxide/polymethyl methacrylate gel polymer dielectric under 50-70 ℃ 60-80 ℃ of stirred in water bath;
Above-mentioned each component is mixed by following proportioning:
Methyl methacrylate MMA:20-30g
Silicon-dioxide: 2～8g
Organic electrolyte solution: 20-50g
Diisopropyl azodicarboxylate: 0.04-0.1g.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101887803A (en) * | 2010-06-23 | 2010-11-17 | 东莞万利信新材料元件有限公司 | Ultrahigh pressure large-scale aluminum electrolytic capacitor and driving electrolyte thereof |
| TWI562434B (en) * | 2010-09-24 | 2016-12-11 | Sekisui Chemical Co Ltd | Electrolyte, electrolytic solution, gel electrolyte, electrolyte film, a method for producing gel electrolyte cell and lithium-ion secondary cell |
| CN102231330A (en) * | 2011-04-02 | 2011-11-02 | 中国科学院过程工程研究所 | Nano composite polymer electrolyte and preparation method thereof |
| CN102134363B (en) * | 2011-04-12 | 2012-11-21 | 中国科学院合肥物质科学研究院 | Polymethylmethacrylate nanometer composite material and preparation method thereof |
| CN102604135B (en) * | 2012-03-02 | 2014-06-18 | 上海交通大学 | Preparation method of polymethyl methacrylate/titanium dioxide nano-grade composite material |
| CN103881019A (en) * | 2012-12-19 | 2014-06-25 | 上海雷磁传感器科技有限公司 | Gel type solid polymer electrolyte and application thereof |
| CN103441301B (en) * | 2013-09-11 | 2017-09-12 | 东莞新能源科技有限公司 | Lithium ion battery gel electrolyte and preparation method thereof |
| CN111477952B (en) * | 2018-01-03 | 2022-02-25 | 清陶（昆山）能源发展有限公司 | Polyacrylate solid polymer electrolyte, preparation method and application thereof in solid lithium battery |
| CN111196888B (en) * | 2020-01-06 | 2020-12-11 | 浙江大学 | Gel polymer electrolyte doped with modified particles and preparation method and application thereof |
| CN117673644A (en) * | 2023-12-29 | 2024-03-08 | 盐山万路达科技有限公司 | Gel polymer electrolyte membrane and preparation method and application thereof |
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| 新型凝胶聚合物电解质的合成与性能. 齐，力，董绍俊.高等学校化学学报，第26卷第11期. 2005 |
| 新型凝胶聚合物电解质的合成与性能. 齐，力，董绍俊.高等学校化学学报，第26卷第11期. 2005 * |
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