CN105761947A - Preparation method of composite gel polymer electrolyte - Google Patents

Preparation method of composite gel polymer electrolyte Download PDF

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Publication number
CN105761947A
CN105761947A CN201610261909.1A CN201610261909A CN105761947A CN 105761947 A CN105761947 A CN 105761947A CN 201610261909 A CN201610261909 A CN 201610261909A CN 105761947 A CN105761947 A CN 105761947A
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China
Prior art keywords
gel polymer
polymer electrolyte
composite gel
preparation
plasticizer
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CN201610261909.1A
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Chinese (zh)
Inventor
李素敏
张旭东
江徽
张钊
孙林
冷京航
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Jiangsu University
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Jiangsu University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
    • 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
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses a preparation method of a composite gel polymer electrolyte. An epoxy-resin-based electrolyte and a mesoporous TiO2 carry out recombination so as to prepare the composite gel polymer electrolyte. The composite gel polymer electrolyte prepared in the invention possesses high room temperature ion conductivity and good electrochemical stability. An electrochemical window is more than 5V. And simultaneously good mechanical strength is possessed. A synthesis technology is simple and easy to perform. The method is suitable for a super capacitor.

Description

A kind of preparation method of composite gel polymer electrolyte
Technical field
The invention belongs to technical field of electronic materials, the preparation method being specifically related to a kind of composite gel polymer electrolyte for ultracapacitor.
Background technology
Gel polymer electrolyte is a kind of new functional macromolecule material, both there is the good processing characteristics of solid polymer electrolyte and security performance, there is again the conductivity at room temperature that conventional liquid electrolyte is higher, be mainly used in the energy storage devices such as ultracapacitor, lithium rechargeable battery and solaode.Current research concentrates on that polyethylene glycol oxide (PEO) is, polyacrylonitrile (PAN) is, polymethyl methacrylate (PMMA) is be with Kynoar (PVDF).Along with energy storage device application day by day deep, the performance of gel polymer electrolyte is faced with new challenges, and not only to possess higher conductivity at room temperature and wider electrochemical stability window, also to possess good mechanics mechanical strength and heat-resistant stability.The new type gel polymer dielectric that exploitation has the high comprehensive performance such as high intensity, high ionic conductivity is significant for the development in this field.
Polymer has broad, the performance of easy-regulating and the stronger designability of polyreaction, functional polymer, conducting polymer, block copolymers etc. become the electrolytical ideal chose of high-strength gel, copolymerization, blended, compounds etc. become the important means of regulation and control gel polymer electrolyte electrochemistry and mechanical property, as passed through to adopt linear structure polymer with cross-linked structure polymer copolymerization or blended method performance of control (J.Compos.Mater., 2013, 47 (22): 1-8), the polymer of linear molecule chain structure is beneficial to ion transmission, improve ionic conductivity, and cross-linked structure polymer is beneficial to raising mechanical strength.Research proves, the mechanical property of gel polymer electrolyte and chemical property can be regulated and controled by modification mode such as copolymerization, blended, compounds, but, chemical property and mechanical strength often restrict mutually, how the basis of electrolyte electrochemical performance to be improved its mechanical strength become Research Challenges, electrochemistry and mechanical property and be optimized to as important subject simultaneously not reducing.Polyethyleneglycol diglycidylether belongs to aliphatic glycidyl ether epoxy resin, strand is linear structure, it is rich in good pliability, it is beneficial to raising ionic conductivity, and cross-linking reaction can be carried out with epoxide group, form tridimensional network, be beneficial to the electrolytical mechanical strength of raising, belong to a kind of Multifunction structure electrolysis matter.Adopt mesoporous TiO2It is composite modified, be remarkably improved electrolytical combination property (Li Sumin. the preparation of structure-accumulation energy type carbon fiber/epoxy resin based composites and performance study [D]. Jiangsu: Jiangsu University, 2014), but, electrolytical ionic conductivity needs to be improved further.
Summary of the invention
The preparation method that it is an object of the invention to provide a kind of composite gel polymer electrolyte, the composite gel polymer electrolyte making preparation has higher conductivity at room temperature and broader electrochemical stability window, and makes its electrochemical stability, mechanical performance be improved.
For solving above-mentioned technical problem, the concrete technical scheme that the present invention adopts is as follows:
A kind of composite gel polymer electrolyte, by polymeric matrix, electrolytic salt, plasticizer and mesoporous TiO2Composition, it is characterised in that mesoporous TiO2After interpolation, placement certain time makes its nano pore adsorbing electrolyte saline solution, then prepares with firming agent crosslinking curing then through polymeric matrix, specifically includes following steps:
Step one, by dissolving electrolyte salt in plasticizer, prepares electrolyte salt solution；
Step 2, by mesoporous TiO2Add in above-mentioned electrolyte salt solution, after ultrasonic 20min, stir 2～3h, place 1～3d, make mesoporous TiO2Nano pore adsorbing electrolyte saline solution, obtains mixture；
Step 3, under stirring condition, adds polymeric matrix in said mixture, is subsequently adding firming agent, 60～90 DEG C of heating 20～30min, obtains homogeneous viscous solution；
Step 4, moves into mould by viscous solution, and be heating and curing under 80 DEG C of conditions 8～12h, namely obtains composite gel polymer electrolyte；
Described mesoporous TiO2BET specific surface area be 264m2/ g, average pore size is 4.3nm, mesoporous TiO26～8wt.% that addition is electrolytic salt, plasticizer, polymeric matrix and firming agent gross mass.
Described polymeric matrix is polyethyleneglycol diglycidylether epoxy resin (PEGDGE), and the addition of PEGDGE is the 40～50% of electrolytic salt, plasticizer, polymeric matrix and firming agent gross mass.
Described electrolytic salt is tetraethyl ammonium tetrafluoroborate (C2H5)4NBF4Or tetrabutyl hexafluorophosphoric acid amine (TBAPF6), the concentration of wherein said electrolytic salt is 0.8～1.0mol/l.
Described plasticizer is Allyl carbonate, the one of ethylene carbonate or its mixture, and the addition of plasticizer is the 30～40% of electrolytic salt, plasticizer, polymeric matrix and firming agent gross mass.
Described firming agent is triethylene tetramine (TEtA), and wherein TEtA:PEGDGET mass ratio is 1:5.
The present invention has beneficial effect.The present invention, with epoxy resin for matrix, adopts mesoporous TiO2Modified preparation composite gel polymer electrolyte, cross linking of epoxy resin makes mesoporous TiO before solidifying2Nano pore being filled a certain amount of electrolyte salt solution, is adsorbed with the nano pore of electrolyte salt solution and is more beneficial for ion in duct, carries out fast transferring, thus becoming the important channel of ion transmission, more effective improve ionic conductivity.Gained composite gel polymer electrolyte has excellent combination property, therefore has wider application prospect.
Accompanying drawing explanation
Fig. 1 is mesoporous TiO used in the present invention2TEM figure；
Fig. 2 is the SEM figure of composite gel polymer electrolyte in the present invention.
Detailed description of the invention
It is further elucidated with present disclosure below in conjunction with specific embodiment, but these embodiments are not limiting as protection scope of the present invention.
Embodiment 1
By 1.0g tetrabutyl hexafluorophosphoric acid amine solvent in 3.87g Allyl carbonate, prepare electrolyte salt solution, by mesoporous for 0.58g TiO2Add in above-mentioned saline solution, ultrasonic 20min, stirs 2h, places 1d, obtain mixture；Under stirring condition, 4g polyethyleneglycol diglycidylether is added in mixed liquor, is subsequently adding 0.8g triethylene tetramine, 90 DEG C of heating 30min, obtain homogeneous viscous solution；Viscous solution is moved into mould, and be heating and curing under 80 DEG C of conditions 8h, namely obtains composite gel polymer electrolyte.Mesoporous TiO used2TEM scheme as shown in Figure 1.The SEM of composite gel polymer electrolyte schemes as shown in Figure 2.
Embodiment 2
By 1.0g tetrabutyl hexafluorophosphoric acid amine solvent in 3.87g Allyl carbonate, prepare electrolyte salt solution, by mesoporous for 0.68g TiO2Add in above-mentioned saline solution, ultrasonic 20min, stirs 3h, places 2d, obtain mixture；Under stirring condition, 4g polyethyleneglycol diglycidylether is added in mixture, is subsequently adding 0.8g triethylene tetramine, 90 DEG C of heating 20min, obtain homogeneous viscous solution；Viscous solution is moved into mould, and be heating and curing under 80 DEG C of conditions 8h, namely obtains composite gel polymer electrolyte.
Embodiment 3
By 1.25g tetrabutyl hexafluorophosphoric acid amine solvent in 3.87g Allyl carbonate, prepare electrolyte salt solution, by mesoporous for 0.77g TiO2Add in above-mentioned saline solution, ultrasonic 20min, stirs 2h, places 2d, obtain mixture；Under stirring condition, 6.4g polyethyleneglycol diglycidylether is added in mixture, is subsequently adding 1.28g triethylene tetramine, 60 DEG C of heating 30min, obtain homogeneous viscous solution；Viscous solution is moved into mould, and be heating and curing under 80 DEG C of conditions 10h, namely obtains composite gel polymer electrolyte.
Embodiment 4
By 1.25g tetrabutyl hexafluorophosphoric acid amine solvent in 3.87g Allyl carbonate, prepare electrolyte salt solution, by mesoporous for 0.89g TiO2Add in above-mentioned saline solution, ultrasonic 20min, stirs 2h, places 3d, obtain mixture；Under stirring condition, 5g polyethyleneglycol diglycidylether is added in mixed liquor, is subsequently adding 1g triethylene tetramine, 75 DEG C of heating 30min, obtain homogeneous viscous solution；Viscous solution is moved into mould, and be heating and curing under 80 DEG C of conditions 10h, namely obtains composite gel polymer electrolyte.
Embodiment 5
By 1.25g tetrabutyl hexafluorophosphoric acid amine solvent in 3.87g Allyl carbonate, prepare saline solution, by mesoporous for 0.79g TiO2Add in above-mentioned saline solution, ultrasonic 20min, stirs 2h, places 3d, obtain mixture；Under stirring condition, 3.94g polyethyleneglycol diglycidylether is added in mixed liquor, is subsequently adding 0.79g triethylene tetramine, 80 DEG C of heating 30min, obtain homogeneous viscous solution；Viscous solution is moved into mould, and be heating and curing under 80 DEG C of conditions 12h, namely obtains composite gel polymer electrolyte.
Embodiment 6
0.63g tetraethyl ammonium tetrafluoroborate is dissolved in 3.87g Allyl carbonate and ethylene carbonate mixed solvent in (volume ratio is 1:1), prepares electrolyte salt solution, by mesoporous for 0.74g TiO2Add in above-mentioned saline solution, ultrasonic 20min, stirs 3h, stands 1d, obtain mixture；Under stirring condition, 4.4g polyethyleneglycol diglycidylether is added in mixture, is subsequently adding 0.88g triethylene tetramine, 85 DEG C of heating 25min, obtain homogeneous viscous solution；Viscous solution is moved into mould, and be heating and curing under 80 DEG C of conditions 10h, namely obtains composite gel polymer electrolyte.
The performance of the composite gel polymer electrolyte system that the embodiment above obtains is as shown in table 1.
The performance of the composite gel polymer electrolyte that each embodiment of table 1. obtains

Claims (6)

1. the preparation method of a composite gel polymer electrolyte, it is characterised in that: mesoporous TiO2After interpolation, placement certain time makes its nano pore adsorbing electrolyte saline solution, then prepares with firming agent crosslinking curing then through polymeric matrix, specifically includes following steps:
Step one, by dissolving electrolyte salt in plasticizer, prepares to obtain electrolyte salt solution；
Step 2, by mesoporous TiO2Add in described electrolyte salt solution, after supersound process 20min, stir 2～3h, place 1～3d, make mesoporous TiO2Nano pore adsorbing electrolyte saline solution, obtains mixture；
Step 3, under stirring condition, adds polymeric matrix in described mixture, is subsequently adding firming agent, heats 20～30min, obtain homogeneous viscous solution under 60～90 DEG C of conditions；
Step 4, moves into mould by described viscous solution, and be heating and curing 8～12h under 80 DEG C of conditions, namely obtains composite gel polymer electrolyte.
2. the preparation method of a kind of composite gel polymer electrolyte according to claim 1, it is characterised in that: described mesoporous TiO2BET specific surface area be 264m2/ g, average pore size is 4.3nm, mesoporous TiO26～8wt.% that addition is described electrolytic salt, described plasticizer, described polymeric matrix and described firming agent gross mass.
3. the preparation method of a kind of composite gel polymer electrolyte according to claim 1, it is characterized in that: described polymeric matrix is the addition of polyethyleneglycol diglycidylether epoxy resin PEGDGE, PEGDGE is the 40～50% of electrolytic salt, plasticizer, polymeric matrix and firming agent gross mass.
4. the preparation method of a kind of composite gel polymer electrolyte according to claim 1, it is characterised in that: described electrolytic salt is tetraethyl ammonium tetrafluoroborate (C2H5)4NBF4Or tetrabutyl hexafluorophosphoric acid amine (TBAPF6) in any one, the concentration of described electrolytic salt is 0.8～1.0mol/l.
5. the preparation method of a kind of composite gel polymer electrolyte according to claim 1, it is characterized in that: described plasticizer is the mixture of the one or both in Allyl carbonate, ethylene carbonate, the addition of plasticizer is the 30～40% of electrolytic salt, plasticizer, polymeric matrix and firming agent gross mass.
6. the preparation method of a kind of composite gel polymer electrolyte according to claim 1, it is characterised in that: described firming agent is triethylene tetramine (TEtA), and wherein TEtA:PEGDGET mass ratio is 1:5.
CN201610261909.1A 2016-04-25 2016-04-25 Preparation method of composite gel polymer electrolyte Pending CN105761947A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109037774A (en) * 2018-07-30 2018-12-18 哈尔滨工业大学无锡新材料研究院 A kind of crosslinked polymer electrolyte and preparation method thereof suitable for lithium secondary battery
CN109192355A (en) * 2018-05-30 2019-01-11 江苏大学 A kind of solid conduction gel and preparation method thereof suitable for electrochemical system
CN109473716A (en) * 2018-11-01 2019-03-15 深圳清华大学研究院 Lithium ion battery polymer electrolyte film and preparation method thereof
CN109616697A (en) * 2018-11-01 2019-04-12 深圳清华大学研究院 Magnesium ion battery polymer dielectric film and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101183727A (en) * 2007-12-06 2008-05-21 哈尔滨工业大学 All solid state electrolyte and preparing method and application of the same
CN101409365A (en) * 2008-11-19 2009-04-15 华南师范大学 Lithium ion battery gel polymer electrolyte doped with nanometer particle and preparation method thereof
CN101621134A (en) * 2009-06-23 2010-01-06 华南师范大学 Gel polymer lithium ion battery electrolyte, preparation method and application thereof
CN101662041A (en) * 2008-08-29 2010-03-03 深圳市比克电池有限公司 Method for preparing gel polymer lithium ion battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101183727A (en) * 2007-12-06 2008-05-21 哈尔滨工业大学 All solid state electrolyte and preparing method and application of the same
CN101662041A (en) * 2008-08-29 2010-03-03 深圳市比克电池有限公司 Method for preparing gel polymer lithium ion battery
CN101409365A (en) * 2008-11-19 2009-04-15 华南师范大学 Lithium ion battery gel polymer electrolyte doped with nanometer particle and preparation method thereof
CN101621134A (en) * 2009-06-23 2010-01-06 华南师范大学 Gel polymer lithium ion battery electrolyte, preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李素敏: "结构储能型碳纤维/环氧树脂基复合材料的制备及性能研究", 《中国博士学位论文全文数据库-工程科技I辑》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109192355A (en) * 2018-05-30 2019-01-11 江苏大学 A kind of solid conduction gel and preparation method thereof suitable for electrochemical system
CN109037774A (en) * 2018-07-30 2018-12-18 哈尔滨工业大学无锡新材料研究院 A kind of crosslinked polymer electrolyte and preparation method thereof suitable for lithium secondary battery
CN109037774B (en) * 2018-07-30 2020-10-09 哈尔滨工业大学无锡新材料研究院 Crosslinked polymer electrolyte suitable for lithium secondary battery and preparation method thereof
CN109473716A (en) * 2018-11-01 2019-03-15 深圳清华大学研究院 Lithium ion battery polymer electrolyte film and preparation method thereof
CN109616697A (en) * 2018-11-01 2019-04-12 深圳清华大学研究院 Magnesium ion battery polymer dielectric film and preparation method thereof

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Application publication date: 20160713