CN103247447A - Polyelectrolyte film for super capacitor and preparation method thereof - Google Patents

Polyelectrolyte film for super capacitor and preparation method thereof Download PDF

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CN103247447A
CN103247447A CN201210408010XA CN201210408010A CN103247447A CN 103247447 A CN103247447 A CN 103247447A CN 201210408010X A CN201210408010X A CN 201210408010XA CN 201210408010 A CN201210408010 A CN 201210408010A CN 103247447 A CN103247447 A CN 103247447A
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solvent
film
sediment
preparation
ultracapacitor
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严锋
仇波
林本才
钱文静
司志红
顾凤楼
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Suzhou University
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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
    • 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
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    • Y02E60/13—Energy storage using capacitors

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Abstract

The invention discloses a polyelectrolyte film for a super capacitor and a preparation method thereof. The preparation method comprises the following steps: adding ionic liquid monomer, initiator and solvent I in a reaction vessel, followed by heating and reacting for 1-3 hours under the protection of blown inert gas to obtain products subjected to sedimentation, washing and drying; then dissolving the products in water to perform anion exchange with KPF6 or NaBF4 to obtain a sediment subjected to washing and drying; dissolving the sediment in a solvent II to prepare a solution placed in a polytetrafluoroethylene plate; and finally heating to evaporate the solvent II to obtain the film, and then assembling the film on the super capacitor with the specific capacitance up to 65 F/g. Due to the adoption of the technical scheme, the method is simple, easy to operate, suitable for industrialized production, and solves the defects that a traditional liquid electrolyte is difficult to assemble and easy to leak; and meanwhile, the film can be made to be in various shapes and plays the role of a diaphragm. Besides, the film lower in cost, and is suitable for portable electronic products.

Description

A kind of ultracapacitor polyelectrolyte membrane and preparation method
Technical field
The present invention relates to a kind of ultracapacitor parts and preparation method thereof, be specifically related to a kind of ultracapacitor polyelectrolyte membrane and preparation method thereof.
Background technology
Ultracapacitor mainly is made up of electrode, electrolyte, barrier film, and wherein electrolyte mainly plays the transmission ion.Ultracapacitor mainly exists [Adv. Mater. 2012,24,5130-5135 with liquid, solid-state form with electrolyte; J. Phys. Chem. C 2012,116 (27), 14179 – 14187].Along with continuous progress in science and technology, high-tech product is gradually towards microminiaturization, ultra-thinization, intelligent direction development; For electric power being provided for these products, the ultracapacitor conduct is a kind of power supply apparatus wherein, also should stride forward towards microminiaturization, ultra-thinization, portability direction.Yet this moment, liquid electrolyte can not adapt to this requirement because there being shortcomings such as difficult, the easy leakage of encapsulation.Polymer dielectric is as a kind of solid electrolyte, because it has the effect that polymer easily is cast as the film shape, the characteristics that easily are processed to different shape can play barrier film simultaneously, reduced cost, and caused extensive concern.
In recent years, because ionic liquid has zero vapour pressure, electrochemical window is wide, heat-resistant stability is high, conductivity advantages of higher [Acc. Chem. Res. 2007,40,1165-1173], be applied to assembling the ultracapacitor of larger volume as electrolyte.Poly ion liquid combines ionic liquid simultaneously and has the advantage that high conductance and polymer are easy to be processed into different shape, has broad prospects in the ultracapacitor field.
Put down in writing a kind of method for preparing poly ion liquid in the existing document: in reactor, add imidazole type ion liquid, solvent, initator, under the protection of inert gas, back flow reaction, obtain product, then it is carried out anion exchange [Journal of Polymer Science:Part A:Polymer Chemistry, 2004,42,208-212; 2009,47,746-753], but products therefrom is not cast into film.
Summary of the invention
The objective of the invention is to overcome the above problem that prior art exists, a kind of ultracapacitor polyelectrolyte membrane and preparation method thereof is provided.
For realizing above-mentioned technical purpose, reach above-mentioned technique effect, the present invention is achieved through the following technical solutions:
A kind of ultracapacitor polyelectrolyte membrane and preparation method thereof may further comprise the steps:
1) in reaction vessel, add ionic liquid monomer, initator, solvent 1, feeding under the inert gas shielding, add thermal response 1-3 hour, obtain product;
2) with the product that obtains through precipitation, washing, drying, be dissolved in the water subsequently and KPF 6Perhaps NaBF 4Carry out anion exchange, obtain sediment;
3) with the sediment that obtains again through washing, drying, the sediment that obtains is dissolved in solvent 2, be mixed with solution, place on the polyfluortetraethylene plate, heating evaporation solvent 2 is made film, and the gained film is assembled into ultracapacitor, it reaches as high as 65F/g than electric capacity.
Further, the ionic liquid monomer in the described step (1) is the ionic liquid of polymerizable imidazole type
Figure DEST_PATH_567786DEST_PATH_IMAGE001
，
Figure DEST_PATH_646600DEST_PATH_IMAGE002
，
Figure DEST_PATH_144577DEST_PATH_IMAGE003
，
Figure DEST_PATH_650645DEST_PATH_IMAGE004
Figure DEST_PATH_804546DEST_PATH_IMAGE005
In one or several, m=0-10 wherein, p=0-6, q=0-5, y=6-11, z=4-7; X is respectively I, Br, Cl, SCN, N (CN) 2, C (CN) 3, B (CN) 4, CF 3SO 3, C 2F 5SO 3, [N (SO 2CF 3) 2], CF 3Among the COO one or several.
Further, the described solvent 1 in the described step (1) is hydrophilic solvents such as water, ethanol, methyl alcohol; Described solvent 2 in the described step (3) is carrene, chloroform, N, hydrophobic solvents such as dinethylformamide.
The invention has the beneficial effects as follows:
Adopt technical solution of the present invention, a series of novel polyelectrolyte membranes that are used for ultracapacitor have been designed, this electrolyte has overcome conventional liquid electrolyte encapsulation shortcoming difficult, that easily leak, simultaneously can be processed into different shape, play the effect of barrier film, reduced cost, be applicable to that portable type electronic product and this method are simple, easy operating is applicable to suitability for industrialized production.
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technological means of the present invention, and can be implemented according to the content of specification, below with preferred embodiment of the present invention describe in detail as after.The specific embodiment of the present invention is provided in detail by following examples.
Embodiment
Below in conjunction with embodiment, describe the present invention in detail.
A kind of ultracapacitor polyelectrolyte membrane and preparation method thereof may further comprise the steps:
1) in reaction vessel, add ionic liquid monomer, initator, solvent 1, feeding under the inert gas shielding, add thermal response 1-3 hour, obtain product;
2) with the product that obtains through precipitation, washing, drying, be dissolved in the water subsequently and KPF 6Perhaps NaBF 4Carry out anion exchange, obtain sediment;
3) with the sediment that obtains again through washing, drying, the sediment that obtains is dissolved in solvent 2, be mixed with solution, place on the polyfluortetraethylene plate, heating evaporation solvent 2 is made film, and the gained film is assembled into ultracapacitor, it reaches as high as 65F/g than electric capacity.
Further, the ionic liquid monomer in the described step (1) is the ionic liquid of polymerizable imidazole type
，
Figure DEST_PATH_39535DEST_PATH_IMAGE002
， ，
Figure DEST_PATH_357701DEST_PATH_IMAGE004
In one or several, m=0-10 wherein, p=0-6, q=0-5, y=6-11, z=4-7; X is respectively I, Br, Cl, SCN, N (CN) 2, C (CN) 3, B (CN) 4, CF 3SO 3, C 2F 5SO 3, [N (SO 2CF 3) 2], CF 3Among the COO one or several.
Further, the described solvent 1 in the described step (1) is hydrophilic solvents such as water, ethanol, methyl alcohol; Described solvent 2 in the described step (3) is carrene, chloroform, N, hydrophobic solvents such as dinethylformamide.
Embodiment one:
Figure DEST_PATH_250888DEST_PATH_IMAGE006
1g, initator 0.01g, water 50ml is as in the reaction vessel, at N 2Protection was reacted one hour down, and product is soluble in water and KPF after precipitation, washing, drying 6Carry out anion exchange, the sediment that obtains through washing, drying, is dissolved in solvent N with the sediment that obtains again, and dinethylformamide is mixed with solution, places on the polyfluortetraethylene plate, and the heating evaporation solvent is made film.Film and the electrode of preparation are assembled into ultracapacitor, record it and reach 50F/g than electric capacity.
Embodiment two:
Figure DEST_PATH_98758DEST_PATH_IMAGE007
1g, initator 0.01g, water 50ml is as in the reaction vessel, at N 2Protection was reacted one hour down, and product is soluble in water and NaBF after precipitation, washing, drying 4Carry out anion exchange, the sediment that obtains through washing, drying, is dissolved in solvent N with the sediment that obtains again, and dinethylformamide is mixed with solution, places on the polyfluortetraethylene plate, and the heating evaporation solvent is made film.Film and the electrode of preparation are assembled into ultracapacitor, record it and reach 55F/g than electric capacity.
Embodiment three:
1g, initator 0.01g, water 50ml is as in the reaction vessel, at N 2Protection was reacted one hour down, and product is soluble in water and KPF after precipitation, washing, drying 6Carry out anion exchange, the sediment that obtains through washing, drying, is dissolved in solvent N with the sediment that obtains again, and dinethylformamide is mixed with solution, places on the polyfluortetraethylene plate, and the heating evaporation solvent is made film.Film and the electrode of preparation are assembled into ultracapacitor, record it and reach 51F/g than electric capacity.
Embodiment four:
Figure DEST_PATH_185980DEST_PATH_IMAGE009
1g, initator 0.01g, water 50ml is as in the reaction vessel, at N 2Protection was reacted one hour down, and product is soluble in water and NaBF after precipitation, washing, drying 4Carry out anion exchange, the sediment that obtains through washing, drying, is dissolved in solvent N with the sediment that obtains again, and dinethylformamide is mixed with solution, places on the polyfluortetraethylene plate, and the heating evaporation solvent is made film.Film and the electrode of preparation are assembled into ultracapacitor, record it and reach 53F/g than electric capacity.
Embodiment five:
Figure DEST_PATH_513056DEST_PATH_IMAGE010
1g, initator 0.01g, water 50ml is as in the reaction vessel, at N 2Protection was reacted one hour down, and product is soluble in water and KPF after precipitation, washing, drying 6Carry out anion exchange, the sediment that obtains through washing, drying, is dissolved in solvent N with the sediment that obtains again, and dinethylformamide is mixed with solution, places on the polyfluortetraethylene plate, and the heating evaporation solvent is made film.Film and the electrode of preparation are assembled into ultracapacitor, record it and reach 56F/g than electric capacity.
Embodiment six:
Figure DEST_PATH_797407DEST_PATH_IMAGE011
1g, initator 0.01g, water 50ml is as in the reaction vessel, at N 2Protection was reacted one hour down, and product is soluble in water and NaBF after precipitation, washing, drying 4Carry out anion exchange, the sediment that obtains through washing, drying, is dissolved in solvent N with the sediment that obtains again, and dinethylformamide is mixed with solution, places on the polyfluortetraethylene plate, and the heating evaporation solvent is made film.Film and the electrode of preparation are assembled into ultracapacitor, record it and reach 58F/g than electric capacity.
Embodiment seven:
Figure DEST_PATH_646152DEST_PATH_IMAGE012
0.5g, initator 0.005g, water 50ml is as in the reaction vessel, at N 2Protection was reacted one hour down, and product is soluble in water and KPF after precipitation, washing, drying 6Carry out anion exchange, the sediment that obtains through washing, drying, is dissolved in solvent N with the sediment that obtains again, and dinethylformamide is mixed with solution, places on the polyfluortetraethylene plate, and the heating evaporation solvent is made film.Film and the electrode of preparation are assembled into ultracapacitor, record it and reach 55F/g than electric capacity.
Embodiment eight:
Figure DEST_PATH_408571DEST_PATH_IMAGE013
0.8g, initator 0.008g, water 50ml is as in the reaction vessel, at N 2Protection was reacted one hour down, and product is soluble in water and NaBF after precipitation, washing, drying 4Carry out anion exchange, the sediment that obtains through washing, drying, is dissolved in solvent N with the sediment that obtains again, and dinethylformamide is mixed with solution, places on the polyfluortetraethylene plate, and the heating evaporation solvent is made film.Film and the electrode of preparation are assembled into ultracapacitor, record it and reach 56F/g than electric capacity.
Embodiment nine:
Figure DEST_PATH_590154DEST_PATH_IMAGE014
1.5g, initator 0.015g, water 50ml is as in the reaction vessel, at N 2Protection was reacted one hour down, and product is soluble in water and KPF after precipitation, washing, drying 6Carry out anion exchange, the sediment that obtains through washing, drying, is dissolved in solvent N with the sediment that obtains again, and dinethylformamide is mixed with solution, places on the polyfluortetraethylene plate, and the heating evaporation solvent is made film.Film and the electrode of preparation are assembled into ultracapacitor, record it and reach 60F/g than electric capacity.
Embodiment ten:
Figure DEST_PATH_45406DEST_PATH_IMAGE015
2g, initator 0.02g, water 50ml is as in the reaction vessel, at N 2Protection was reacted one hour down, and product is soluble in water and NaBF after precipitation, washing, drying 4Carry out anion exchange, the sediment that obtains through washing, drying, is dissolved in solvent N with the sediment that obtains again, and dinethylformamide is mixed with solution, places on the polyfluortetraethylene plate, and the heating evaporation solvent is made film.Film and the electrode of preparation are assembled into ultracapacitor, record it and reach 65F/g than electric capacity.
The above only for the preferred embodiment of invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (3)

1. ultracapacitor polyelectrolyte membrane and preparation method thereof may further comprise the steps:
1) in reaction vessel, add ionic liquid monomer, initator, solvent 1, feeding under the inert gas shielding, add thermal response 1-3 hour, obtain product;
2) with the product that obtains through precipitation, washing, drying, be dissolved in the water subsequently and KPF 6Perhaps NaBF 4Carry out anion exchange, obtain sediment;
3) with the sediment that obtains again through washing, drying, the sediment that obtains is dissolved in solvent 2, be mixed with solution, place on the polyfluortetraethylene plate, heating evaporation solvent 2 is made film, and the gained film is assembled into ultracapacitor, it reaches as high as 65F/g than electric capacity.
2. ultracapacitor polyelectrolyte membrane according to claim 1 and preparation method thereof is characterized in that, the ionic liquid monomer in the described step (1) is the ionic liquid of polymerizable imidazole type
Figure RE-985018DEST_PATH_IMAGE001
，
Figure RE-898748DEST_PATH_IMAGE002
，
Figure RE-439450DEST_PATH_IMAGE003
，
Figure RE-82921DEST_PATH_IMAGE004
In one or several, m=0-10 wherein, p=0-6, q=0-5, y=6-11, z=4-7; X is respectively I, Br, Cl, SCN, N (CN) 2, C (CN) 3, B (CN) 4, CF 3SO 3, C 2F 5SO 3, [N (SO 2CF 3) 2], CF 3Among the COO one or several.
3. ultracapacitor polyelectrolyte membrane according to claim 1 and preparation method thereof is characterized in that, the described solvent 1 in the described step (1) is hydrophilic solvents such as water, ethanol, methyl alcohol; Described solvent 2 in the described step (3) is carrene, chloroform, N, hydrophobic solvents such as dinethylformamide.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105949367A (en) * 2016-05-11 2016-09-21 常州大学 Polymer electrolyte film adopting hydrophilic/hydrophobic interpenetrating network structure and preparation method of film

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102167759A (en) * 2010-12-27 2011-08-31 东莞宏强电子有限公司 Preparation method of ionic liquid, products and application thereof

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
CN102167759A (en) * 2010-12-27 2011-08-31 东莞宏强电子有限公司 Preparation method of ionic liquid, products and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
A.LEWANDOWSKI等: "Electrochemical capacitors with polymer electrolytes based on ionic liquids", 《SOLID STATE IONICS》 *
REBECA MARCILLA等: "Tuning the Solubility of Polymerized Ionic Liquids by Simple Anion-Exchange Reactions", 《JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY》 *
张海朗等: "离子液体聚合物电解质的制备和电导率", 《2006年中国固态离子学既国际电动汽车动力技术研讨会论文摘要集》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105949367A (en) * 2016-05-11 2016-09-21 常州大学 Polymer electrolyte film adopting hydrophilic/hydrophobic interpenetrating network structure and preparation method of film
CN105949367B (en) * 2016-05-11 2019-03-22 常州大学 A kind of hydrophilic/hydrophobic inierpeneirating network structure polymer dielectric film and preparation method thereof

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Application publication date: 20130814