CN100589218C - Supercapacitor with inner polymerization type gel polymer electrolyte and preparation process thereof - Google Patents
Supercapacitor with inner polymerization type gel polymer electrolyte and preparation process thereof Download PDFInfo
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- CN100589218C CN100589218C CN 200510010303 CN200510010303A CN100589218C CN 100589218 C CN100589218 C CN 100589218C CN 200510010303 CN200510010303 CN 200510010303 CN 200510010303 A CN200510010303 A CN 200510010303A CN 100589218 C CN100589218 C CN 100589218C
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- polymer electrolyte
- gel polymer
- capacitor
- liclo
- mass ratio
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
This invention provides an inner-polymerization gel polymer electrolyte super capacitor and its technique; wherein, the technique comprises, overlaying and wrapping the prepared positive polarity, membrane and negative polarity to put into capacitor shell; preparing solution with some polymer monomer, plasticizer, electrolyte salt and a little initiator to inject into the prepared positive and negative polarities, heating at 65Deg for a plurality of hours and forming gel. The product has high conductivity of 8~11X10<-3>S.cm<-1> and specific capacitor value of 24.29F/g(i=0.5mA/cm2).
Description
Technical field
The present invention relates to electrochemical field and adopt interior gathering gel polymer electrolyte ultracapacitor and technology.
Background technology
Ultracapacitor has the big and high advantage of chemical power source energy resource density of physical capacitor power density concurrently, is a kind of efficient, practical novel energy.By energy storage mechanism, be divided into double electric layer capacitor and redox pseudo-capacitance device.Ultracapacitor has high power density, long cycle life, and fast charging rate can be used for the center accessory power supply of electronic memory circuit, high-power out-put supply, the power supply of compact electric apparatus or the pulse power etc. are particularly useful for the hybrid power source of electric automobile.
Ultracapacitor can be divided into the water system electrolyte by electrolyte, organic bath and polymer dielectric capacitor.The water system electrolytic condenser limits because of the decomposition voltage that is subjected to water, and its operating voltage is about 1 volt; Though and the organic electrolyte capacitor operating voltage can reach more than 4 volts, there is leakage problem; Polymer dielectric capacitor not only operating voltage is higher, and safety, nothing leaks, and is convenient to capacitor and develops to miniature, ultrathin, special-shaped direction.It is divided into solid polymer electrolyte capacitor and gel polymer electrolyte capacitor again, and the room-temperature conductivity of solid polymer electrolyte is low, has only 10
-9～10
-5Scm
-1, poor practicability, the room-temperature conductivity of gel polymer electrolyte reaches 10
-3S.cm
-1The order of magnitude.But the preparation of at present general gel polymer electrolyte capacitor is earlier gel polymer electrolyte to be made film, again with both positive and negative polarity stack assembling, it exists the contradiction of gel polymer electrolyte conductivity and intensity and electrolyte and porous electrode contact poor, and the problem of complicated process of preparation.And add barrier film in the preparation process of the gel polymer electrolyte capacitor of the interior gathering among the present invention in addition, and therefore less demanding to strength problem, can reduce the content of polymer monomer greatly, improve the conductivity of gel polymer electrolyte; And electrolyte is to inject when liquid condition in the capacitor, aggregates into gel polymer electrolyte then, and electrolyte is better with contacting of porous electrode, and preparation technology is simple.Can be referring to documents: A.Lewandowski, M.Galinski, M.Krzyzanowski.New polymer electrolyte poly (acrylonitrile)-sulpholane-(C2H5) 4NBF4 forchemical capacitors[J] .Solid State Ionics, 2003,158:367-373.
Summary of the invention
The present invention is that polymerization prepares the gel polymer electrolyte capacitor in adopting, and to reach the content that reduces polymer monomer, improves the conductivity of gel polymer electrolyte; And electrolyte is to inject when liquid condition in the capacitor, aggregates into gel polymer electrolyte then, can increase electrolyte and contacting that electrode material surface is amassed; And simplified preparation technology.
Formation of the present invention (seeing accompanying drawing 1) is made up of the gel polymer electrolyte (4) that is contained in the positive and negative electrode (2) in the housing (1) and be placed on the barrier film (3) between the positive and negative electrode (2) and adopt interior polymerization methods to make.
Preparation technology of the present invention: at first with active carbon: acetylene black: LA132: CMC was by 84: 5: 10: 1 mass ratio mixes, and blade coating after 100 ℃ of dryings of vacuum, is made the positive and negative electrode (2) of the about 100 μ m of thickness under 10MPa pressure on aluminium foil.
Again positive and negative electrode (2) and the barrier film (3) for preparing superposeed, reels, in the capacitor casing of packing into (1).The electrolytic salt LiClO that drying is good
4Or LiPF
6Or (C
2H
5)
4NBF
4Be dissolved in plasticizer dimethyl carbonate (DMC): ethylene carbonate (EC)=1: 1～1.5 (mass ratioes) or propene carbonate (PC): ethylene carbonate (EC)=1: 1～1.5 (mass ratioes) or methyl ethyl carbonate (EMC): in the solution of ethylene carbonate (EC)=1: 1～1.5 (mass ratioes), the concentration of electrolytic salt is 0.5～1.5mol/L, afterwards acrylonitrile (AN) is added in the solution of being made up of electrolytic salt and plasticizer, wherein the quality percentage composition of AN is 10%～20%, add a small amount of initator again, inject capacitor (1) in the lump, sealing.Afterwards 65 ℃ down heating a few hours form gels, this moment, acrylonitrile polymerization became polyacrylonitrile (PAN), then made the have gel polymer electrolyte ultracapacitor (seeing accompanying drawing 1) of (4).Adopt cyclic voltammetric, the internal gathering gel polymer electrolyte of galvanostatic charge capacitor to carry out performance test.
The method of measurement of gel polymer electrolyte conductivity: two stainless steel electrodes that will have certain area and distance place above-mentioned electrolyte, sealing, heat a few hours formation gel polymer electrolyte down at 65 ℃, adopt the conductivity of AC impedence method test gel polymer electrolyte.
The PAN+1mol/LLiClO that makes with said method
4The room-temperature conductivity of/DMC+EC gel polymer electrolyte (4) is 9.76mScm
-1, PAN+1mol/LLiClO
4The room-temperature conductivity of/PC+EC gel polymer electrolyte (4) is 8.23mScm
-1, PAN+1mol/LLiClO
4The room-temperature conductivity of/EMC+EC gel polymer electrolyte (4) is 11.50mScm
-1, far above gel polymer electrolyte make film conductivity (with reference to the data of gained by experiment in the documents, see the table 1 in the documents, its conductivity range for O.518～4.46mScm
-1).
Can see not having significantly reaction peak in 2.5V from the cyclic voltammogram (seeing accompanying drawing 2) of gel polymer electrolyte capacitor, have the electric current platform of broad, figure is near rectangle, and what generation was described mainly is electric double layer capacitance.Curve 1 in the accompanying drawing 2 is represented PAN+1mol/LLiClO
4The cyclic voltammetry curve of/DMC+EC gel polymer electrolyte capacitor; Curve 2 in the accompanying drawing 2 is represented PAN+1mol/L LiClO
4The cyclic voltammetry curve of/PC+EC gel polymer electrolyte capacitor; Curve 3 in the accompanying drawing 2 is represented PAN+1mol/LLiClO
4The cyclic voltammetry curve of/EMC+EC gel polymer electrolyte capacitor; Abscissa among the figure is the voltage of capacitor, and unit is V, and ordinate is the electric current of capacitor, and unit is A.
The specific volume value that obtains capacitor by constant current charge-discharge test is respectively 21.100,20.574,24.294F/g (i=0.5mA/cm
2).As seen PAN+1mol/LLiClO
4The specific capacity of the capacitor of/EMC+EC gel polymer electrolyte is bigger.
By the explanation of foregoing, interior gathering gel polymer electrolyte ultracapacitor has the conductivity height of gel polymer electrolyte among the present invention, and electrolyte contacts better the simple advantage of preparation technology with electrode material surface is long-pending.
Description of drawings
Fig. 1 is the structural representation of interior gathering gel polymer electrolyte ultracapacitor;
Fig. 2 is 3 kinds of PAN base gel polymer electrolyte ultracapacitor cyclic voltammetry curve figure (sweep speed is 5mV/s).
Embodiment
Example 1: with active carbon: acetylene black: LA132: CMC was by 84: 5: 10: 1 mass ratio mixes, and blade coating after 100 ℃ of dryings of vacuum, is made the positive and negative electrode (2) of the about 100 μ m of thickness under 10MPa pressure on aluminium foil.
Again positive and negative electrode (2) and the barrier film (3) for preparing superposeed, reels, in the capacitor casing of packing into (1).The LiClO that drying is good
4Be dissolved in DMC: EC=1: in the solution of 1 (mass ratio), LiClO
4Concentration is 1mol/L, afterwards acrylonitrile (AN) and a small amount of initator is added by electrolytic salt LiClO
4With plasticizer DMC: EC=1: in the solution that 1 (mass ratio) formed, wherein AN accounts for 10%, in the capacitor that reinjects (1), sealing.Afterwards 65 ℃ down heating a few hours form gels, make the have gel polymer electrolyte ultracapacitor of (4).
The room-temperature conductivity that adopts AC impedence method to record this gel polymer electrolyte (4) is 9.76mScm
-1, make the conductivity (with reference to documents) of film far above gel polymer electrolyte.Can see not having significantly reaction peak in 2.5V from the cyclic voltammetry curve figure (seeing accompanying drawing 2) of gel polymer electrolyte capacitor, have the electric current platform of broad, figure is near rectangle, and what generation was described mainly is electric double layer capacitance.The specific volume value that obtains capacitor by the constant current charge-discharge test is 21.10F/g (i=0.5mA/cm
2).
Example 2: with active carbon: acetylene black: LA132: CMC was by 84: 5: 10: 1 mass ratio mixes, and blade coating after 100 ℃ of dryings of vacuum, is made the positive and negative electrode (2) of the about 100 μ m of thickness under 10MPa pressure on aluminium foil.
Again positive and negative electrode (2) and the barrier film (3) for preparing superposeed, reels, in the capacitor casing of packing into (1).The LiClO that drying is good
4Be dissolved in EMC: EC=1: in the solution of 1 (mass ratio), LiClO
4Concentration is 1mol/L, afterwards acrylonitrile (AN) and a small amount of initator is added by electrolytic salt LiClO
4With plasticizer EMC: EC=1: in the solution that 1 (mass ratio) formed, wherein AN accounts for 10%, in the capacitor that reinjects (1), sealing.Afterwards 65 ℃ down heating a few hours form gels, make the have gel polymer electrolyte ultracapacitor of (4).
The room-temperature conductivity that adopts AC impedence method to record this gel polymer electrolyte (4) is 11.50mScm
-1, make the conductivity (with reference to documents) of film far above gel polymer electrolyte.Can see not having significantly reaction peak in 2.5V from the cyclic voltammetry curve figure (seeing accompanying drawing 2) of gel polymer electrolyte capacitor, have the electric current platform of broad, figure is near rectangle, and what generation was described mainly is electric double layer capacitance.The specific volume value that obtains capacitor by the constant current charge-discharge test is 24.29F/g (i=0.5mA/cm
2).
Gathering gel polymer electrolyte ultracapacitor has the conductivity height of gel polymer electrolyte among the present invention, can reach 8～11 * 10
-3Scm
-1, the specific volume value of capacitor reaches 24.29F/g (i=0.5mA/cm
2) and the simple advantage of preparation technology.
Claims (1)
1. the preparation technology of gathering gel polymer electrolyte ultracapacitor in a kind is characterized in that:
With active carbon: acetylene black: LA132: CMC was by 84: 5: 10: 1 mass ratio mixes, and blade coating after 100 ℃ of dryings of vacuum, is made the positive and negative electrode (2) of thickness 100 μ m under 10MPa pressure on aluminium foil;
Again positive and negative electrode (2) and the barrier film (3) for preparing superposeed, reels, in the capacitor casing of packing into (1), the LiClO that drying is good
4Being dissolved in mass ratio is methyl ethyl carbonate: in the solution of ethylene carbonate=1: 1, and LiClO
4Concentration is 1mol/L, afterwards acrylonitrile and a small amount of initator is added in the solution of being made up of electrolytic salt and plasticizer, and described plasticizer is that mass ratio is a methyl ethyl carbonate: ethylene carbonate=1: 1, described electrolytic salt is LiClO
4, wherein acrylonitrile quality percentage composition is 10%, in the capacitor that reinjects (1), sealing, afterwards 65 ℃ down heating a few hours form gels, make the have gel polymer electrolyte ultracapacitor of (4).
Priority Applications (1)
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|---|---|---|---|
| CN 200510010303 CN100589218C (en) | 2005-09-05 | 2005-09-05 | Supercapacitor with inner polymerization type gel polymer electrolyte and preparation process thereof |
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|---|---|---|---|
| CN 200510010303 CN100589218C (en) | 2005-09-05 | 2005-09-05 | Supercapacitor with inner polymerization type gel polymer electrolyte and preparation process thereof |
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|---|---|
| CN1734690A CN1734690A (en) | 2006-02-15 |
| CN100589218C true CN100589218C (en) | 2010-02-10 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101582334B (en) * | 2009-06-08 | 2011-03-30 | 清华大学 | Supercapacitor based on active carbon electrode and manufacturing method thereof |
| CN101656155B (en) * | 2009-09-22 | 2012-02-22 | 南京双登科技发展研究院有限公司 | Method for making high-capacity organic ultracapacitor in flexible package |
| WO2017097175A1 (en) | 2015-12-09 | 2017-06-15 | Huawei Technologies Co., Ltd. | System, method and nodes for performance measurement in segment routing network |
| FR3064812B1 (en) * | 2017-04-03 | 2022-06-24 | Nawatechnologies | METHOD FOR MANUFACTURING ELECTROCHEMICAL CAPACITOR |
| CN113096969A (en) * | 2021-04-09 | 2021-07-09 | 南京大学 | Polymer gel electrolyte-electrode and preparation method thereof, super capacitor and preparation method thereof |
-
2005
- 2005-09-05 CN CN 200510010303 patent/CN100589218C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| New polymer electrolyte poly(acrylonitrile)–sulpholane–(C2H5)4NBF4 for chemical capacitors. A. Lewandowski et al.Solid State Ionics,Vol.158 . 2003 |
| New polymer electrolyte poly(acrylonitrile)–sulpholane–(C2H5)4NBF4 for chemical capacitors. A. Lewandowski et al.Solid State Ionics,Vol.158 . 2003 * |
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