CN101131887A - Ionic liquid containing cupric salt and method for preparing the same - Google Patents
Ionic liquid containing cupric salt and method for preparing the same Download PDFInfo
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- CN101131887A CN101131887A CNA2007100623341A CN200710062334A CN101131887A CN 101131887 A CN101131887 A CN 101131887A CN A2007100623341 A CNA2007100623341 A CN A2007100623341A CN 200710062334 A CN200710062334 A CN 200710062334A CN 101131887 A CN101131887 A CN 101131887A
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- ionic liquid
- salt
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- electric capacity
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Abstract
A kind of ionic liquid containing Cu2+ salt is composed of Cu2+ salt and ionic liquid with the molar ratio of 1:1-9.The Cu2+ salt of 1-4 times amount of its solubility in ionic liquid are dissolved in the ionic liquid for 1-9 days, and the new ionic liquid are filtered and separated out. The present invention has the advantages of simple in preparation process, high in capacitance and steady in large-current charge/discharge.
Description
Technical field
The present invention relates to a kind of Cu of containing
2+Ionic liquid and preparation method thereof.
Background technology
Ionic liquid (Ionic Liquid) claims room temperature fuse salt (aRoom TemperatureMolten Salt) again, is in room temperature or the organic liquid material of being made up of ion fully under near the condition of room temperature.It has advantages such as conductivity height, electrochemical window are wide, non-volatile, not flammable, Heat stability is good.Therefore be widely used in the electronic components such as Li ion secondary battery, solar cell, electrochemical capacitor.
Ionic liquid has bright development prospect as the electrolyte of electrochemical capacitor, yet, mobile poor because pure ionic liquid viscosity at ambient temperature is bigger, cause the capacitance of capacitor not high.Article " Activated carbons anddouble layer capacitance " (Electrochimica Acta, 41 (1996) 1633-1639) as Hang Shi has been introduced with 30%KOH and has been made electrolyte, and specific area is 875m
2The active carbon of/g is 94F/g as the ratio electric capacity that electrode obtains.And A.Lewandowski etc. adopt the active carbon of close specific area, with ionic liquid [EMIm] BF
4The ratio electric capacity that obtains as electrolyte only is 55F/F (Solid State Ionics 161 (2003) 243-249).As seen, ionic liquid do electrolyte resulting than electric capacity much smaller than aqueous electrolyte.So the researcher reaches the purpose of raising than electric capacity by reducing ion liquid viscosity.The way that organic solvent (acetonitrile, propene carbonate, gamma-butyrolacton) is added in employings such as Tetsuo Nishida reduces ion liquid viscosity, reached the purpose that improves capacitance, but made capacitor in use increase inflammable and explosive danger coefficient (J.Fluorme Chem.120 (2003) 135-141).Discoveries such as A.Balducci also can reach the purpose that reduces viscosity of il, improves capacitance by improving temperature, but this has limited the range of application that capacitor is worked at ambient temperature (J.PowerSources 165 (2007) 922-927).
Goal of the invention
It is good to the purpose of this invention is to provide a kind of security performance, applied range and the Cu that contains of big electric capacity can be provided
2+The ionic liquid of salt and preparation method.
Embodiment
The Cu that contains of the present invention2+The ionic liquid of salt is by Cu2+Salt and ionic liquid are pressed Cu2+: from Sub-liquid mol ratio is 1: 1-9 forms.
Aforesaid Cu2+Salt comprises copper sulphate (CuSO4), copper nitrate (Cu (NO3)
2), copper chloride (CuCl2), copper acetate (Cu (CH3COO)
2) or cupric oxalate (C2CuO
4) in One or more.
Described ionic liquid is to be selected from 1-ethyl-3-methyl imidazolium tetrafluoroborate ([EMIm] BF
4), 1-ethyl-3-methylimidazole perchlorate ([EMIm] ClO
4), 1-ethyl-3-N-Methylimidazoleacetic salt ([EMIm] CH
3COO), 1-ethyl-3-methylimidazole trifluoroacetate ([EMIm] CF
3COO), 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIm] BF
4) or 1-butyl-3-methylimidazole hexafluorophosphate ([BMIm] PF
6) in one or more.
Preparation method of the present invention is as follows:
Under the vacuum condition with Cu
2+Salt is doubly measured with the 1-4 of its solubility in ionic liquid and was dissolved in the ionic liquid 1～9 day, filters to isolate ionic liquid.
The Cu that contains of the present invention
2+The ionic liquid of salt can be applied in the electrode material of mixture of carbon nanotube, charcoal-aero gel, active carbon, activated carbon fiber, nano carbon fiber and different materials.
Advantage of the present invention is:
Contain Cu
2+The ionic liquid of salt has advantages such as security performance is good, applied range, capacitance characteristic is good, capacitance is high, preparation technology is simple.
Embodiment
Embodiment 1
Cu is dissolved in 10g[EMIm with the 15g metal] BF
4In, in vacuum, placed 8 days under the room temperature, isolate ionic liquid, Cu with husky worry funnel
2+With [EMIm] BF
4Mol ratio reach 1: 1.Adopt active carbon to do electrode material, carry out the constant current charge-discharge experiment, promptly at 25 ℃, under the condition of 2 volts of upper voltage limits, 0 volt of lower voltage limit, 2 milliamperes of constant currents, carry out charge/discharge repeatedly, after 50 circulations, obtaining than electric capacity is 190F/g.Pure ionic liquid [EMIm] BF of metal ion not
4, testing its ratio electric capacity as capacitor electrolyte is 118F/g.
Embodiment 2
With 9g CuSO
4Be dissolved in 2g[EMIm] CF
3COO, 4g[EMIm] BF
4And 4g[EMIm] ClO
4Mixed electrolytic solution in, in vacuum, placed 7 days under the room temperature, isolate ionic liquid, Cu with husky worry funnel
2+With [EMIm] CF
3The mol ratio of COO reaches 1: 2.Adopt charcoal-aero gel to do electrode material, carry out the constant current charge-discharge experiment, promptly at 25 ℃, under the condition of 2 volts of upper voltage limits, 0 volt of lower voltage limit, 2 milliamperes of constant currents, carry out charge/discharge repeatedly, after 50 circulations, obtaining than electric capacity is 138F/g.Pure ionic liquid [EMIm] CF of metal ion not
3COO, testing its ratio electric capacity as capacitor electrolyte is 85F/g.
Embodiment 3
With 4g Cu (NO
3)
2With 3.6g CuCl
2Mixture be dissolved in 10g[EMIm] ClO
4In, in vacuum, placed 6 days under the room temperature, isolate ionic liquid, Cu with husky worry funnel
2+With [EMIm] ClO
4Mol ratio reach 1: 3.Adopt carbon nanotube to do electrode material, carry out the constant current charge-discharge experiment, promptly at 25 ℃, under the condition of 2 volts of upper voltage limits, 0 volt of lower voltage limit, 2 milliamperes of constant currents, carry out charge/discharge repeatedly, after 50 circulations, obtaining than electric capacity is 130F/g.Pure ionic liquid [EMIm] ClO of metal ion not
4, testing its ratio electric capacity as capacitor electrolyte is 80F/g.
Embodiment 4
With 3.8g CuCl
2Be dissolved in 10g[EMIm] CH
3Among the COO, in vacuum, placed 5 days under the room temperature, isolate ionic liquid, Cu with husky worry funnel
2+With [EMIm] CH
3The mol ratio of COO reaches 1: 4.Adopt activated carbon fiber to do electrode material, carry out the constant current charge-discharge experiment, promptly at 25 ℃, under the condition of 2 volts of upper voltage limits, 0 volt of lower voltage limit, 2 milliamperes of constant currents, carry out charge/discharge repeatedly, after 50 circulations, obtaining than electric capacity is 152F/g.Pure ionic liquid [EMIm] CH of metal ion not
3COO, testing its ratio electric capacity as capacitor electrolyte is 89F/g.
Embodiment 5
With 5g Cu (CH
3COO)
2Be dissolved in 10g[BMIm] BF
4In, in vacuum, placed 4 days under the room temperature, isolate ionic liquid, Cu with husky worry funnel
2+With [BMIm] BF
4Mol ratio reach 1: 5.Adopt nano carbon fiber to do electrode material, carry out the constant current charge-discharge experiment, promptly at 25 ℃, under the condition of 2 volts of upper voltage limits, 0 volt of lower voltage limit, 2 milliamperes of constant currents, carry out charge/discharge repeatedly, after 50 circulations, obtaining than electric capacity is 123F/g.Pure ionic liquid [BMIm] BF of metal ion not
4, testing its ratio electric capacity as capacitor electrolyte is 90F/g.
Embodiment 6
16g Cu is dissolved in 5g[EMIm] BF
4And 5g[BMIm] PF
6Mixed liquor in, in vacuum, placed 3 days under the room temperature, isolate ionic liquid, Cu with husky worry funnel
2+With [BMIm] PF
6/ [EMIm] BF
4The mol ratio of mixed liquor reaches 1: 6.Adopt active carbon to do electrode material, carry out the constant current charge-discharge experiment, promptly at 25 ℃, under the condition of 2 volts of upper voltage limits, 0 volt of lower voltage limit, 2 milliamperes of constant currents, carry out charge/discharge repeatedly, after 50 circulations, obtaining than electric capacity is 129F/g.The ionic liquid of metal ion [BMIm] PF not
6/ [EMIm] BF
4, testing its ratio electric capacity as capacitor electrolyte is 93F/g.
Embodiment 7
With 7g Cu and 6g C
2CuO
4Mixture be dissolved in 2g[EMIm] BF
4And 8g[BMIm] BF
4Mixed liquor in, in vacuum, placed 2 days under the room temperature, isolate ionic liquid, Cu with husky worry funnel
2+With [EMIm] BF
4/ [BMIm] BF
4Mol ratio reach 1: 7.Adopt active carbon and activated carbon fiber composite material (mass ratio 1: 1) to do electrode, carry out the constant current charge-discharge experiment, promptly at 25 ℃, under the condition of 2 volts of upper voltage limits, 0 volt of lower voltage limit, 2 milliamperes of constant currents, carry out charge/discharge repeatedly, after 50 circulations, obtaining than electric capacity is 123F/g.The ionic liquid of metal ion [EMIm] BF not
4/ [BMIm] BF
4, testing its ratio electric capacity as capacitor electrolyte is 118F/g.
Embodiment 8
With 3.8g Cu and 1.2g CuSO
4Mixture be dissolved in 1g[EMIm] BF
4And 9g[EMIm] ClO
4Mixed liquor in, in vacuum, placed 1.5 days under the room temperature, isolate ionic liquid, Cu with husky worry funnel
2+With [EMIm] BF
4/ [EMIm] ClO
4Mol ratio reach 1: 8.Adopt carbon nanotube and charcoal-aero gel composite material (mass ratio 1: 5) to do electrode, carry out the constant current charge-discharge experiment, promptly at 25 ℃, under the condition of 2 volts of upper voltage limits, 0 volt of lower voltage limit, 2 milliamperes of constant currents, carry out charge/discharge repeatedly, after 50 circulations, obtaining than electric capacity is 139F/g.The ionic liquid of metal ion [EMIm] BF not
4/ [EMIm] ClO
4, testing its ratio electric capacity as capacitor electrolyte is 118F/g.
Embodiment 9
With 6g Cu and 10g CuCl
2Mixture be dissolved in 9g[BMIm] BF
4And 1g[EMIm] CF
3In the mixed liquor of COO, in vacuum, placed 1 day under the room temperature, isolate ionic liquid, Cu with husky worry funnel
2+With [EMIm] BF
4/ [EMIm] CF
3The mol ratio of COO reaches 1: 9.Adopt charcoal-aero gel and nano carbon fiber (mass ratio 1: 9) to do electrode, carry out the constant current charge-discharge experiment under 80 ℃, under the condition of 2 volts of upper voltage limits, 0 volt of lower voltage limit, 2 milliamperes of constant currents, carry out charge/discharge repeatedly, after 50 circulations, obtaining than electric capacity is 98F/g.Contain Cu
2+Ionic liquid [BMIm] BF
4/ [EMIm] CF
3COO, its ratio electric capacity as capacitor electrolyte of test is 70F/g under the room temperature.
Claims (4)
1. one kind contains Cu
2+The ionic liquid of salt is characterized in that it being by Cu
2+Salt and ionic liquid are pressed Cu
2+: the ionic liquid mol ratio is 1: 1-9 forms.
2. a kind of Cu that contains as claimed in claim 1
2+The ionic liquid of salt is characterized in that described Cu
2+Salt is one or more in copper sulphate, copper nitrate, copper chloride, copper acetate or the cupric oxalate.
3. a kind of Cu that contains as claimed in claim 1
2+The ionic liquid of salt, it is characterized in that described ionic liquid be 1-ethyl-3-methyl imidazolium tetrafluoroborate, 1-ethyl-3-methylimidazole perchlorate, 1-ethyl-3-N-Methylimidazoleacetic salt, 1-ethyl-3-methylimidazole trifluoroacetate, 1-butyl-3-methyl imidazolium tetrafluoroborate or 1-butyl-3-methylimidazole hexafluorophosphate (in one or more.
4. as each described a kind of Cu that contains of claim 1-3
2+The preparation method of ionic liquid of salt is characterized in that under the vacuum condition Cu
2+Salt is doubly measured with the 1-4 of its solubility in ionic liquid and was dissolved in the ionic liquid 1～9 day, filters to isolate ionic liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100623341A CN101131887A (en) | 2007-07-17 | 2007-07-17 | Ionic liquid containing cupric salt and method for preparing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100623341A CN101131887A (en) | 2007-07-17 | 2007-07-17 | Ionic liquid containing cupric salt and method for preparing the same |
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|---|---|
| CN101131887A true CN101131887A (en) | 2008-02-27 |
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|---|---|---|---|
| CNA2007100623341A Pending CN101131887A (en) | 2007-07-17 | 2007-07-17 | Ionic liquid containing cupric salt and method for preparing the same |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102473530A (en) * | 2009-08-03 | 2012-05-23 | 索尼公司 | Electrochemical capacitor |
| CN102760577A (en) * | 2011-04-27 | 2012-10-31 | 海洋王照明科技股份有限公司 | Double-electric layer capacitor electrolyte and double-electric layer capacitor using same |
| CN102760578A (en) * | 2011-04-27 | 2012-10-31 | 海洋王照明科技股份有限公司 | Electrolyte for capacitor and capacitor using electrolyte |
| US8773841B2 (en) | 2008-09-09 | 2014-07-08 | Cap-Xx Limited | Charge storage device |
| CN104479170A (en) * | 2014-11-25 | 2015-04-01 | 上海交通大学 | Method for preparing composite material through ionic liquid modified carbon nano tube |
| CN105609327A (en) * | 2015-12-19 | 2016-05-25 | 湘潭大学 | Porous active carbon/copper ion super-capacitor preparation method |
| CN109378227A (en) * | 2018-11-22 | 2019-02-22 | 西南交通大学 | A kind of solid electrolyte and preparation method thereof and supercapacitor |
-
2007
- 2007-07-17 CN CNA2007100623341A patent/CN101131887A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8773841B2 (en) | 2008-09-09 | 2014-07-08 | Cap-Xx Limited | Charge storage device |
| CN102210000B (en) * | 2008-09-09 | 2015-05-06 | Cap-Xx有限公司 | A charge storage device |
| CN102473530A (en) * | 2009-08-03 | 2012-05-23 | 索尼公司 | Electrochemical capacitor |
| CN102760577A (en) * | 2011-04-27 | 2012-10-31 | 海洋王照明科技股份有限公司 | Double-electric layer capacitor electrolyte and double-electric layer capacitor using same |
| CN102760578A (en) * | 2011-04-27 | 2012-10-31 | 海洋王照明科技股份有限公司 | Electrolyte for capacitor and capacitor using electrolyte |
| CN102760578B (en) * | 2011-04-27 | 2016-05-18 | 海洋王照明科技股份有限公司 | A kind of capacitor electrolyte and use the capacitor of this electrolyte |
| CN104479170A (en) * | 2014-11-25 | 2015-04-01 | 上海交通大学 | Method for preparing composite material through ionic liquid modified carbon nano tube |
| CN105609327A (en) * | 2015-12-19 | 2016-05-25 | 湘潭大学 | Porous active carbon/copper ion super-capacitor preparation method |
| CN105609327B (en) * | 2015-12-19 | 2018-04-03 | 湘潭大学 | A kind of preparation method of porous activated carbon/copper ion ultracapacitor |
| CN109378227A (en) * | 2018-11-22 | 2019-02-22 | 西南交通大学 | A kind of solid electrolyte and preparation method thereof and supercapacitor |
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Open date: 20080227 |