CN102760574A - Electric double layer capacitor electrolyte and electric double layer capacitor using electrolyte - Google Patents
Electric double layer capacitor electrolyte and electric double layer capacitor using electrolyte Download PDFInfo
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- CN102760574A CN102760574A CN201110107430XA CN201110107430A CN102760574A CN 102760574 A CN102760574 A CN 102760574A CN 201110107430X A CN201110107430X A CN 201110107430XA CN 201110107430 A CN201110107430 A CN 201110107430A CN 102760574 A CN102760574 A CN 102760574A
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- layer capacitor
- anion
- ionic liquid
- cation
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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
The invention belongs to the electrochemical field, and discloses an electric double layer capacitor electrolyte and a capacitor using the electrolyte, wherein the electric double layer capacitor electrolyte comprises ionic liquid and C60 or a derivative of C60 at the mass ratio of 1:0.001-1:0.1. The electrolyte for the capacitor provided by the invention is formed through a mixed reaction of the ionic liquid and C60 or the derivative of C60; after the ionic liquid is mixed with C60 or the derivative of C60, C60 is polarized easily in the ionic liquid, and the polarized C60 or the derivative of C60 generates charge separation; therefore, the polarized C60 or the derivative of C60 is attached to the surface of an electrode material, so that electric double layer capacitance is greatly increased; in addition, C60 or the derivative of C60 is cheap and easy to obtain; the solubility of C60 or the derivative of C60 in the ionic liquid is high; and C60 or the derivative of C60 is non-volatile and does not increase an inflammable and explosive danger coefficient as organic addition agents; therefore, the electric double layer capacitor electrolyte and the electric double layer capacitor using the electrolyte are safe and cheap, and the specific capacity of the electric double layer capacitor can be increased greatly.
Description
Technical field
The present invention relates to electrochemical field, relate in particular to a kind of double electric layer capacitor electrolyte.This invention also relates to a kind of capacitor that uses this electrolyte.
Background technology
Double electric layer capacitor is a kind of novel energy storage device, has advantages such as high power density, high cycle life, fast charging and discharging performance be good, is widely used in the AC-battery power source of military field, device for mobile communication, computer and electric automobile etc.As the important component part of double electric layer capacitor, electrolyte has very big influence to the accumulate performance of double electric layer capacitor, is determining the operating voltage range of capacitor, accumulate capacity and working temperature and operational environment.
Ionic liquid is in room temperature or the organic liquid material of being made up of ion fully under near the condition of room temperature.As a kind of novel electrolyte, the application of double electric layer capacitor has been expanded in ion liquid appearance greatly.It has advantages such as conductivity height, electrochemical window are wide, non-volatile, not flammable, Heat stability is good.Ionic liquid has bright development prospect as the electrolyte of double electric layer capacitor, yet pure ionic liquid capacitance at ambient temperature is not high.Adopt the way of adding organic solvent (acetonitrile, propene carbonate, 1-butyrolactone) to reach the purpose that improves capacitance, but make capacitor in use increase inflammable and explosive danger coefficient.
Summary of the invention
The object of the present invention is to provide a kind of safe and reliable, cost is low, and can improve the electrolyte of double electric layer capacitor specific capacity.
Technical scheme of the present invention is following:
A kind of electrolyte solution for electric double layer capacitor, it is by ionic liquid and C
60The or derivatives thereof hybrid reaction forms, ionic liquid and C
60Or derivatives thereof (as, 6-phenyl-6-methyl butyrate-C
61) mass ratio be 1: 0.001～1: 0.1; Preferred ion liquid and C
60The mass ratio of or derivatives thereof is preferably 1: 0.01～and 1: 0.1.
Wherein, described ionic liquid is made up of any one anion in glyoxaline cation and tetrafluoro boric acid anion, hexafluorophosphoric acid anion, two (trifluoromethyl sulphonyl) imines anion, acetate anion, methylsulfuric acid ester anion, trifluoroacetic acid anion, trifluoromethane sulfonic acid anion, dicyanogen methyl isophorone amine anion or the trifluoroacetyl fluoroform sulfonamide anions; And described glyoxaline cation is a kind of in 1-butyl-3-methylimidazole cation, 1-propyl group-3-methylimidazole cation, the 1-ethyl-3-methylimidazole cation.
Wherein, described ionic liquid is made up of any one anion in pyrroles's cation and tetrafluoro boric acid anion, hexafluorophosphoric acid anion, two (trifluoromethyl sulphonyl) imines anion, acetate anion, methylsulfuric acid ester anion, trifluoroacetic acid anion, trifluoromethane sulfonic acid anion, dicyanogen methyl isophorone amine anion or the trifluoroacetyl fluoroform sulfonamide anions; And described pyrroles's cation is a kind of in butyl methyl pyrroles cation, propyl group methylpyrrole cation, the ethyl-methyl pyrroles cation.
Wherein, ionic liquid is 1-butyl-3-methyl imidazolium tetrafluoroborate or butyl methyl pyrroles tetrafluoroborate.
Another object of the present invention is to provide a kind of capacitor that uses above-mentioned electrolyte, this capacitor is a double electric layer capacitor.
Electrolyte for capacitor provided by the invention, it is by ionic liquid and C
60The or derivatives thereof hybrid reaction forms, ionic liquid and C
60After or derivatives thereof mixes, C
60Perhaps its derivative is dissolved in the ionic liquid, because C
60Perhaps its derivative has a large amount of delocalized electrons, in ionic liquid, is polarized the C after the polarization easily
60Perhaps its derivative produces separation of charge, therefore the C after the polarization
60Perhaps its derivative is attached to improving electric double layer capacitance greatly on the electrode material surface; And C
60Perhaps its derivative cheaply is easy to get, and the solubility in ionic liquid is high, and non-volatile, can not increase inflammable and explosive danger coefficient as organic additive; Therefore, safety of the present invention, cheap, and can improve the specific capacity of double electric layer capacitor greatly.
Description of drawings
The charging and discharging curve of the capacitor that Fig. 1 makes for the electrolyte that adopts among the embodiment 1.
Embodiment
A kind of electrolyte solution for electric double layer capacitor, it is formed by ionic liquid and C60 or derivatives thereof hybrid reaction, ionic liquid and C60 or derivatives thereof (as, 6-phenyl-6-methyl butyrate-C
61) mass ratio be 1: 0.001～1: 0.1; The mass ratio of preferred ion liquid and C60 or derivatives thereof is preferably 1: 0.01～and 1: 0.1.
Wherein, described ionic liquid is made up of any one anion in glyoxaline cation and tetrafluoro boric acid anion, hexafluorophosphoric acid anion, two (trifluoromethyl sulphonyl) imines anion, acetate anion, methylsulfuric acid ester anion, trifluoroacetic acid anion, trifluoromethane sulfonic acid anion, dicyanogen methyl isophorone amine anion or the trifluoroacetyl fluoroform sulfonamide anions; And described glyoxaline cation is a kind of in 1-butyl-3-methylimidazole cation, 1-propyl group-3-methylimidazole cation, the 1-ethyl-3-methylimidazole cation.
Wherein, described ionic liquid is made up of any one anion in pyrroles's cation and tetrafluoro boric acid anion, hexafluorophosphoric acid anion, two (trifluoromethyl sulphonyl) imines anion, acetate anion, methylsulfuric acid ester anion, trifluoroacetic acid anion, trifluoromethane sulfonic acid anion, dicyanogen methyl isophorone amine anion or the trifluoroacetyl fluoroform sulfonamide anions; And described pyrroles's cation is a kind of in butyl methyl pyrroles cation, propyl group methylpyrrole cation, the ethyl-methyl pyrroles cation.
Wherein, ionic liquid is 1-butyl-3-methyl imidazolium tetrafluoroborate or butyl methyl pyrroles tetrafluoroborate.
Another object of the present invention is to provide a kind of capacitor that uses above-mentioned electrolyte, this capacitor is a double electric layer capacitor.
Electrolyte for capacitor provided by the invention, it is by ionic liquid and C
60The or derivatives thereof hybrid reaction forms, ionic liquid and C
60After or derivatives thereof mixes, C
60Perhaps its derivative is dissolved in the ionic liquid, because C
60Perhaps its derivative has a large amount of delocalized electrons, in ionic liquid, is polarized the C after the polarization easily
60Perhaps its derivative produces separation of charge, therefore the C after the polarization
60Perhaps its derivative is attached to improving electric double layer capacitance greatly on the electrode material surface; And C
60Perhaps its derivative cheaply is easy to get, and the solubility in ionic liquid is high, and non-volatile, can not increase inflammable and explosive danger coefficient as organic additive; Therefore, safety of the present invention, cheap, and can improve the specific capacity of double electric layer capacitor greatly.
Among the present invention, the test of specific capacity of double-layer capacitor: with the Graphene is electrode material, is electrolyte with each embodiment; Be assembled into button cell, utilize the CHI660A electrochemical workstation that it is carried out the constant current charge-discharge test, record it and compare electric capacity; Promptly under 30 degrees celsius; In charging and discharging voltage 0-3v window ranges, after 50 circulations of constant current repeated charge with charging or discharging current 1A/g, obtain it and compare electric capacity; Than CALCULATION OF CAPACITANCE formula is C=dQ/dV=I/ (dV/dt); Wherein, I represents discharge current density, and V represents discharge voltage, and t represents discharge time.
Below in conjunction with accompanying drawing, further explain is done in preferred embodiment of the present invention.
Embodiment 1
In glove box, with mass ratio 1-butyl-3-methyl imidazolium tetrafluoroborate and C of 1: 0.01
60Mix, and C
60After being dissolved in 1-butyl-3-methyl imidazolium tetrafluoroborate, obtain electrolyte solution for electric double layer capacitor.
It is 58F/g that test draws the ratio electric capacity of using the double electric layer capacitor of electrolyte in the present embodiment, and than the application of pure ionic liquid that records under the equal conditions, promptly the ratio electric capacity of the double electric layer capacitor of 1-butyl-3-methyl imidazolium tetrafluoroborate electrolyte is high by 43.6%.
The charging and discharging curve of the capacitor that Fig. 1 makes for the electrolyte that adopts among the embodiment 1; Wherein, discharge voltage 0-3v, discharging current 1A/g.Chain-dotted line is the electrolyte of present embodiment, and solid line is pure ionic liquid.
Can calculate from the charging and discharging curve of Fig. 1: the ratio electric capacity that the application present embodiment is made the double electric layer capacitor of electrolyte is 58F/g; And the application of pure ionic liquid; The ratio electric capacity that is 1-butyl-3-methyl imidazolium tetrafluoroborate double electric layer capacitor of making electrolyte is 40.4F/g; Test draws the ratio electric capacity of using the double electric layer capacitor of electrolyte in the present embodiment; Than the application of pure ionic liquid that records under the equal conditions, promptly 1-butyl-3-methyl imidazolium tetrafluoroborate is high by 43.6% as the ratio electric capacity of the double electric layer capacitor of electrolyte.
Embodiment 2～56 states list as follows:
Annotate: in the table,
1, A representes ionic liquid, and B representes C
60Or derivatives thereof;
2, exceeding ratio than electric capacity is among the corresponding embodiment, use electrolyte among the corresponding embodiment double electric layer capacitor than the percentage that exceeds of the application of pure ionic liquid that records under the capacity ratio equal conditions as the ratio electric capacity of the double electric layer capacitor of electrolyte;
3, among the embodiment 2～56, various preparation technology's flow processs are identical with embodiment 1 with test condition.
Should be understood that above-mentioned statement to preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with accompanying claims.
Claims (10)
1. a double electric layer capacitor electrolyte is characterized in that, this electrolyte comprises ionic liquid and C
60Or derivatives thereof, said ionic liquid and C
60Or C
60The mass ratio of derivative is 1: 0.001～1: 0.1.
2. double electric layer capacitor electrolyte according to claim 1 is characterized in that, said ionic liquid and C
60Or C
60The mass ratio of derivative is 1: 0.01～1: 0.1.
3. double electric layer capacitor electrolyte according to claim 2 is characterized in that, said C
60Derivative is 6-phenyl-6-methyl butyrate-C
61
4. double electric layer capacitor electrolyte according to claim 1; It is characterized in that said ionic liquid is the ionic liquid that any one anion in glyoxaline cation and tetrafluoro boric acid anion, hexafluorophosphoric acid anion, two (trifluoromethyl sulphonyl) imines anion, acetate anion, methylsulfuric acid ester anion, trifluoroacetic acid anion, trifluoromethane sulfonic acid anion, dicyanogen methyl isophorone amine anion or the trifluoroacetyl fluoroform sulfonamide anions is formed.
5. double electric layer capacitor electrolyte according to claim 4 is characterized in that, said glyoxaline cation is any in 1-butyl-3-methylimidazole cation, 1-propyl group-3-methylimidazole cation or 1-ethyl-3-methylimidazole cation.
6. double electric layer capacitor electrolyte according to claim 1; It is characterized in that said ionic liquid is the ionic liquid that any one anion in pyrroles's cation and tetrafluoro boric acid anion, hexafluorophosphoric acid anion, two (trifluoromethyl sulphonyl) imines anion, acetate anion, methylsulfuric acid ester anion, trifluoroacetic acid anion, trifluoromethane sulfonic acid anion, dicyanogen methyl isophorone amine anion or the trifluoroacetyl fluoroform sulfonamide anions is formed.
7. double electric layer capacitor electrolyte according to claim 6 is characterized in that, said pyrroles's cation is any in butyl methyl pyrroles cation, propyl group methylpyrrole cation or the ethyl-methyl pyrroles cation.
8. double electric layer capacitor electrolyte according to claim 1 is characterized in that, said ionic liquid is 1-butyl-3-methyl imidazolium tetrafluoroborate.
9. double electric layer capacitor electrolyte according to claim 1 is characterized in that, said ionic liquid is a butyl methyl pyrroles tetrafluoroborate.
10. a double electric layer capacitor is characterized in that, this capacitor comprises the arbitrary described electrolyte of claim 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110107430.XA CN102760574B (en) | 2011-04-27 | 2011-04-27 | A kind of double electric layer capacitor electrolytic solution and use the double electric layer capacitor of this electrolyte |
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|---|---|---|---|
| CN201110107430.XA CN102760574B (en) | 2011-04-27 | 2011-04-27 | A kind of double electric layer capacitor electrolytic solution and use the double electric layer capacitor of this electrolyte |
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| CN102760574A true CN102760574A (en) | 2012-10-31 |
| CN102760574B CN102760574B (en) | 2015-08-26 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103833621A (en) * | 2012-11-26 | 2014-06-04 | 海洋王照明科技股份有限公司 | Pyrrole ionic liquid, and preparation method and application thereof |
| CN105646186A (en) * | 2016-02-14 | 2016-06-08 | 陈铭 | Ionic liquid adopting methanofullerene carboxylate radicals as anions and preparation method |
| CN105977056A (en) * | 2016-07-05 | 2016-09-28 | 王方茂 | Fullerene super capacitance battery and preparation method thereof |
| CN116404256A (en) * | 2023-05-31 | 2023-07-07 | 宁德时代新能源科技股份有限公司 | Electrolyte, battery monomer, battery and electric equipment |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103833621A (en) * | 2012-11-26 | 2014-06-04 | 海洋王照明科技股份有限公司 | Pyrrole ionic liquid, and preparation method and application thereof |
| CN103833621B (en) * | 2012-11-26 | 2016-08-03 | 海洋王照明科技股份有限公司 | Pyrrole ionic liquid and its preparation method and application |
| CN105646186A (en) * | 2016-02-14 | 2016-06-08 | 陈铭 | Ionic liquid adopting methanofullerene carboxylate radicals as anions and preparation method |
| CN105977056A (en) * | 2016-07-05 | 2016-09-28 | 王方茂 | Fullerene super capacitance battery and preparation method thereof |
| CN116404256A (en) * | 2023-05-31 | 2023-07-07 | 宁德时代新能源科技股份有限公司 | Electrolyte, battery monomer, battery and electric equipment |
| CN116404256B (en) * | 2023-05-31 | 2023-10-27 | 宁德时代新能源科技股份有限公司 | Electrolyte, battery monomer, battery and electric equipment |
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| CN102760574B (en) | 2015-08-26 |
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