CN103682434B - A kind of preparation method of gel type ionic liquid/polymer electrolyte - Google Patents

A kind of preparation method of gel type ionic liquid/polymer electrolyte Download PDF

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Publication number
CN103682434B
CN103682434B CN201310466565.4A CN201310466565A CN103682434B CN 103682434 B CN103682434 B CN 103682434B CN 201310466565 A CN201310466565 A CN 201310466565A CN 103682434 B CN103682434 B CN 103682434B
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ionic liquid
polymer electrolyte
polymer
gel type
peo
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CN103682434A (en
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沙茂林
冯佳
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Hefei Normal University
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Hefei Normal University
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • 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

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Conductive Materials (AREA)
  • Secondary Cells (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

The invention discloses a kind of preparation method of gel type ionic liquid/polymer electrolyte, it is uniformly mixed PEO and nano silicon, joins in acetonitrile, after fully dissolving, adds ionic liquid EMIPF 6, after fully stirring, be poured in clean glass sheet, natural evaporation film forming in dry environment, vacuumize, obtains gel type ionic liquid/polymer electrolyte.The present invention adopts imidazoles organic cation ionic liquid EMIPF6 as plasticizer, and is incorporated in the middle of polymer dielectric, and compound obtains gel-type polymer electrolyte, has both the advantage of ionic liquid and polymer dielectric, and Nano-meter SiO_2 2add the degree of crystallinity not only reducing polymer, also the mobility of live particle is accelerated, conductivity is increased, thus make polymer dielectric thermal stability and chemical property good, the stability of battery and fail safe can be allowed to be greatly improved, to allow chemical power source have very large development prospect.

Description

A kind of preparation method of gel type ionic liquid/polymer electrolyte
Technical field
The present invention relates to a kind of preparation method of gel type ionic liquid/polymer electrolyte.
Background technology
Polymer dielectric (Polymerelectrolyte) refers to a class high polymer ion conductor, containing can dissociative ionic group in its linkage unit, can be divided into anion, cation, double ion conductor.Its molecular structure has chain, pectination and netted, as poly(ethylene oxide) (PEO), polymethyl methacrylate (PMMA) etc.The conductivity of polymer dielectric is good, and there is the feature of macromolecular material, as good springiness, easily formation is membranaceous, quality light, and good processability makes them have a wide range of applications in solid lithium battery, electrochromic device, high capacity capacitor.Gel-type polymer electrolyte because having higher conductivity, and has the stability feature of solid electrolyte, and is considered to the electrolyte system having application prospect in solid lithium ion battery most.Gel-type polymer electrolyte is primarily of polymeric matrix, and electrolytic salt (ionophore) and organic solution Plasticising system are formed.
Ionic liquid (Ionicliquid) is also known as room temperature molten salt (Roomtemperaturemoltensalts), ionic liquid at room temperature (Roomtemperatureionicliquid), organic ion liquid (Organicionicliquids) etc., refer to the material be made up of ion be in a liquid state under room temperature or near room temperature temperature, wherein only there is free anions and canons, without electric neutrality molecule.In ionic compound, the active force between zwitterion is Coulomb force, and amount of charge and the radius of its size and zwitterion are relevant, and ionic radius is larger, and the active force between them is less, and the fusing point of this ionic compound is lower.Ionic liquid is classified: divide according to its organic cation, have imidazoles, pyridines, quaternary ammonium salts and quaternary phosphonium salt.Wherein the ionic liquid of imidazoles is the most stable, as 1-ethyl-3-methylimidazole hexafluorophosphate (EMIPF6), 1-methyl-3-ethyl imidazol(e) tetrafluoro boric acid (EMIBF4).Divide according to organic anion, have metal species and non-metal kind, metal species is as CuC1 2 -, AlCl 4 -, non-metal kind is as BF 4 -, N (CF 3cF 2sO 2) 2 -, PF 6 -.Generally speaking, metal species is responsive to water and air, and non-metal kind is stablized water and air.
Traditional organic solvent is volatile, and thermal stability is not very desirable, and Suitable ranges is narrow, affects the useful life of chemical power source, and is unfavorable for its high-temperature working performance, there is very large shortcoming.And ionic liquid/polymer electrolyte possesses the advantage of ionic liquid and polymer dielectric simultaneously, conductivity is high, electrochemical window is wide, solvent evaporates phenomenon is there is not in wider temperature range, and it is nonflammable, environmentally friendly, the safety and stability of battery is all further enhanced.Develop this kind of novel ionic liquid/polymer electrolyte, be expected to solve some problems existing for traditional electrolyte matter.In recent years, the technology that the direct mixing of employing and situ aggregation method compound prepare the ionic liquid/polymer electrolyte of series of new is increasingly mature, scientific worker, by being incorporated in polymer using synthesized ionic liquid as electrolytic salt and plasticizer, obtains the polymer that a large amount of conductivity is high.Ionic liquid is increasingly deep in the application of photosensitive electro-chemical systems, polymer dielectric film fuel cell, lithium ion battery and double electric layer capacitor, drastically increase the thermal stability of system, chemical stability, conductivity, and the serviceability temperature scope of battery, extend useful life, reduce potential safety hazard, illustrate good application prospect.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of system thermal stability, chemical stability is good, chemical property is excellent gel type ionic liquid/polymer electrolyte.
The present invention adopts imidazoles organic cation ionic liquid EMIPF6 as plasticizer, be introduced in the middle of polymer dielectric, compound obtains gel-type polymer electrolyte, have both the advantage of ionic liquid and polymer dielectric, make its thermal stability and chemical property good, the stability of battery and fail safe can be allowed to be greatly improved, to allow chemical power source have very large development prospect.
The preparation method of a kind of gel type ionic liquid/polymer electrolyte of the present invention, it is fully uniformly mixed PEO and nano silicon, then joins in solvent acetonitrile, stirs and make abundant dissolving; Dissolve completely, add ionic liquid EMIPF 6, after fully stirring, be poured in clean glass sheet, natural evaporation film forming in dry environment, then put into 50-70 DEG C of vacuum drying chamber dry 24 hours, obtain gel type ionic liquid/polymer electrolyte; Described PEO, nano silicon and EMIPF 6mass ratio is 20%-65%:5%-15%:30%-65%.
Preferably, described PEO molecular weight 500000-650000.
Preferably, described PEO, nano silicon and EMIPF 6mass ratio is 40%:10%:50%.
Described poly(ethylene oxide) (PEO) is purchased from the limited branch company in Hefei of traditional Chinese medicines group; Described ionic liquid 1-ethyl-3-methylimidazole hexafluorophosphate (EMIPF 6) purchased from Hangzhou Ke Mo company, analyze pure, 99.5%; Described nano material SiO 2purchased from the limited branch company in Hefei of traditional Chinese medicines group, analyze pure, 99.5%.
PEO at room temperature degree of crystallinity is high, and the present invention adopts nano silicon to mix and enters in macromolecular material polymer, reduce its degree of crystallinity, greatly improves its conductivity.The polymer dielectric prepared is the film like structures of solid-state, surperficial irregularity, and there is a little fine particle centre, if when the content of ionic liquid and nano particle increases; fine particle can be reduced to disappearance; also film can be made even, and fold reduces, surfacing.The degree of crystallinity of polymer and its out-of-flatness close association, the minimizing of fold shows that degree of crystallinity reduces.Conductivity carries out equivalent electric circuit by the energy Qwest figure of measurement to calculate,
In each element of equivalent electric circuit, Rs is required electrolytical impedance magnitude, substitutes into following formula and tries to achieve conductivity.
σ=d/(RsS)
In formula, d is the thickness (cm) of ion liquid polymer dielectric film, and S is the contact area (1cm of electrode and polymer dielectric film 2).
Ionic liquid in the present invention has following effect: one is that two is as plasticizer, and three is the solvents as lithium salts directly as ion source in system.The effect of nano material silicon dioxide: one is SiO 2the ion diffuse that can be in electrolyte of meso-hole structure passage is provided, can obviously improve its ionic conductivity [9], two is the degree of crystallinity that nano particle can reduce PEO.This experiment takes poly(ethylene oxide) (PEO) as polymeric matrix, using ionic liquid as plasticizer and ion source, adds nano material, prepares gel type ionic liquid/polymer electrolyte.Adding of ionic liquid makes the live particle playing electric action in polymer dielectric increase, and conductivity is increased, Nano-meter SiO_2 2add the degree of crystallinity not only reducing polymer, also accelerate the mobility of live particle, conductivity increased.Ionic liquid to mix in polymer in temperature range that obtained gel-type polymer electrolyte makes it wider and no longer includes the volatile phenomenon of solvent by the present invention, the electrochemical stability of battery, fail safe and thermal stability can be improved well, in the middle of lithium ion battery and in other capacitors, have good application prospect.
Accompanying drawing explanation
Fig. 1 is the energy Qwest schematic equivalent circuit of conductivity test.
Embodiment
Following embodiment further illustrates using as the explaination to the technology of the present invention content for content of the present invention; but flesh and blood of the present invention is not limited in described in following embodiment, those of ordinary skill in the art can and should know any simple change based on connotation of the present invention or replace all should belong to protection range of the presently claimed invention.
embodiment 1
By PEO(molecular weight 600000) and nano silicon be fully uniformly mixed, then join in solvent acetonitrile, stir make abundant dissolving; Dissolve completely, add ionic liquid EMIPF 6, after fully stirring, be poured in clean glass sheet, natural evaporation film forming in dry environment, then put into 60 DEG C of vacuum drying chambers dry 24 hours, obtain gel type ionic liquid/polymer electrolyte; Described PEO, nano silicon and EMIPF 6mass ratio is 40%:10%:50%.Gained gel type ionic liquid/polymer electrolyte membrane conductivity 1.41 × 10 -3s.cm -1.
embodiment 2
By PEO(molecular weight 500000) and nano silicon be fully uniformly mixed, then join in solvent acetonitrile, stir make abundant dissolving; Dissolve completely, add ionic liquid EMIPF 6, after fully stirring, be poured in clean glass sheet, natural evaporation film forming in dry environment, then put into 60 DEG C of vacuum drying chambers dry 24 hours, obtain gel type ionic liquid/polymer electrolyte; Described PEO, nano silicon and EMIPF 6mass ratio is 65%:5%:30%.Gained gel type ionic liquid/polymer electrolyte membrane conductivity 1.28 × 10 -3s.cm -1.
embodiment 3
By PEO(molecular weight 650000) and nano silicon be fully uniformly mixed, then join in solvent acetonitrile, stir make abundant dissolving; Dissolve completely, add ionic liquid EMIPF 6, after fully stirring, be poured in clean glass sheet, natural evaporation film forming in dry environment, then put into 60 DEG C of vacuum drying chambers dry 24 hours, obtain gel type ionic liquid/polymer electrolyte; Described PEO, nano silicon and EMIPF 6mass ratio is 20%:15%:65%.Gained gel type ionic liquid/polymer electrolyte membrane conductivity 1.01 × 10 -3s.cm -1.

Claims (1)

1. a preparation method for gel type ionic liquid/polymer electrolyte, is characterized in that, PEO and nano silicon is fully uniformly mixed, and then joins in solvent acetonitrile, stirs and makes abundant dissolving; Dissolve completely, add ionic liquid EMIPF 6, after fully stirring, be poured in clean glass sheet, natural evaporation film forming in dry environment, then put into the 50-70 DEG C of dry 20-30 hour of vacuum drying chamber, obtain gel type ionic liquid/polymer electrolyte; Described PEO, nano silicon and EMIPF 6mass ratio is 40%:10%:50%; Described PEO molecular weight 500000-650000.
CN201310466565.4A 2013-10-09 2013-10-09 A kind of preparation method of gel type ionic liquid/polymer electrolyte Expired - Fee Related CN103682434B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108428931A (en) * 2018-04-17 2018-08-21 中国科学院宁波材料技术与工程研究所 A kind of ion liquid polymer composite solid electrolyte, preparation method and lithium ion battery

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9558894B2 (en) 2011-07-08 2017-01-31 Fastcap Systems Corporation Advanced electrolyte systems and their use in energy storage devices
KR102413496B1 (en) 2011-07-08 2022-06-24 패스트캡 시스템즈 코포레이션 High temperature energy storage device
US10872737B2 (en) 2013-10-09 2020-12-22 Fastcap Systems Corporation Advanced electrolytes for high temperature energy storage device
CN104538670B (en) * 2014-11-24 2017-09-29 深圳华中科技大学研究院 A kind of full solid state polymer electrolyte, its preparation method and application
CN116092839A (en) 2015-01-27 2023-05-09 快帽系统公司 Super capacitor with wide temperature range
WO2016159078A1 (en) * 2015-03-31 2016-10-06 株式会社大阪ソーダ Electrochemical capacitor
CN106970129A (en) * 2017-05-05 2017-07-21 合肥师范学院 A kind of trace element detection device
CN108878966A (en) * 2018-06-12 2018-11-23 天津力神电池股份有限公司 A kind of composite solid electrolyte and preparation method thereof
CN108808079A (en) * 2018-08-01 2018-11-13 广东工业大学 A kind of preparation method of gel electrolyte and its application in field of lithium ion battery
CN111653822B (en) * 2020-06-09 2022-02-11 北京化工大学 Gel type ionic liquid electrolyte for lithium ion battery and preparation method and application thereof
CN114243088A (en) * 2021-11-25 2022-03-25 广州大学 PEO-based composite solid electrolyte and preparation method and application thereof
CN114583256B (en) * 2022-03-08 2023-05-23 中国地质大学（武汉） PEO-LiSS-PIL all-solid electrolyte membrane and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Enhanced Ionic Conductivity of Polymer Electrolytes Containing Nanocomposite SiO2 Particles;Ce-Wen Nan, et al.;《Enhanced Ionic Conductivity of Polymer Electrolytes Containing Nanocomposite SiO2 Particles》;20031231;第91卷;266104-1 *
Ion Conductivity of Polymer Electrolytes Based on PEO Containing Li Salt and Additive Salt;Seok Kim, et al.;《Solid State Phenomena》;20070115;第119卷;119-122 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108428931A (en) * 2018-04-17 2018-08-21 中国科学院宁波材料技术与工程研究所 A kind of ion liquid polymer composite solid electrolyte, preparation method and lithium ion battery
CN108428931B (en) * 2018-04-17 2020-10-09 中国科学院宁波材料技术与工程研究所 Ionic liquid polymer composite solid electrolyte, preparation method thereof and lithium ion battery

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