CN102760576B - A kind of double electric layer capacitor electrolytic solution and use the double electric layer capacitor of this electrolyte - Google Patents
A kind of double electric layer capacitor electrolytic solution and use the double electric layer capacitor of this electrolyte Download PDFInfo
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- CN102760576B CN102760576B CN201110107564.1A CN201110107564A CN102760576B CN 102760576 B CN102760576 B CN 102760576B CN 201110107564 A CN201110107564 A CN 201110107564A CN 102760576 B CN102760576 B CN 102760576B
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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
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Abstract
The invention belongs to electrochemical field, it discloses a kind of double electric layer capacitor electrolytic solution and use the capacitor of this electrolyte; Wherein, the molar concentration of described ferrocene or its derivative is 0.001 ~ 0.02mol/L.Electrolyte for capacitor provided by the invention, is made up of ionic liquid and ferrocene, and wherein the molar concentration of ferrocene is 0.001mol/L to 0.02mol/L.Ferrocene there occurs the redox reaction of high reversible in charge and discharge process, creates faraday's electric capacity, thus substantially increases the ratio capacitance of double electric layer capacitor; And ferrocene is cheaply easy to get, decomposition temperature is high, can not increase inflammable and explosive danger coefficient as organic additive; Therefore, safety of the present invention, cheaply, and can improve the specific capacity of double electric layer capacitor greatly.
Description
Technical field
The present invention relates to electrochemical field, particularly relate to a kind of double electric layer capacitor electrolytic solution.This invention also relates to a kind of capacitor using this electrolyte.
Background technology
Double electric layer capacitor is a kind of novel energy storage device, has the 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 etc. of military field, device for mobile communication, computer and electric automobile.As the important component part of double electric layer capacitor, the accumulate performance of electrolyte to double electric layer capacitor has a significant impact, and decides the operating voltage range of capacitor, accumulate capacity and working temperature and operational environment.
Ionic liquid be room temperature or close to the condition of room temperature under the organic liquid material that is composed entirely of ions.As a kind of novel electrolyte, the appearance of ionic liquid, has expanded the application of double electric layer capacitor greatly.The advantages such as it has that conductivity is high, electrochemical window is wide, non-volatile, non-combustible, Heat stability is good.Ionic liquid has good development prospect as the electrolyte of double electric layer capacitor, but pure ionic liquid capacitance is at ambient temperature not high.Adopt the way of adding organic solvent (acetonitrile, propene carbonate, 1-butyrolactone) to reach the object improving capacitance, but make capacitor in use add 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 as follows:
A kind of electrolyte solution for electric double layer capacitor, it is formed by ionic liquid and ferrocene or derivatives thereof hybrid reaction, described ferrocene or its derivative (as, formyl ferrocene, acetylferrocene, methyl alcohol ferrocene or acetic acid ferrocene) molar concentration be 0.001 ~ 0.02mol/L, the molar concentration of preferred ferrocene or its derivative is 0.005 ~ 0.01mol/L, and more preferably the molar concentration of ferrocene or its derivative is 0.01mol/L.
Wherein, described ionic liquid is made up of any one anion in glyoxaline cation and tetrafluoro boric acid anion, hexafluorophosphoric acid anion, two (trimethyl fluoride sulfonyl) imines anion, acetate anion, methylsulfuric acid ester anion, trifluoroacetic acid anion, trifluoromethane sulfonic acid anion, dicyanogen methyl isophorone amine anion or trifluoroacetyl fluoroform sulfonamide anions; And described glyoxaline cation is the one in 1-butyl-3-methyl imidazolium cation, 1-propyl group-3-methyl imidazolium cation, 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 (trimethyl fluoride sulfonyl) imines anion, acetate anion, methylsulfuric acid ester anion, trifluoroacetic acid anion, trifluoromethane sulfonic acid anion, dicyanogen methyl isophorone amine anion or trifluoroacetyl fluoroform sulfonamide anions; And described pyrroles's cation is the one in butyl methyl pyrroles cation, hydroxypropyl methyl pyrroles cation, 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 using above-mentioned electrolyte, this capacitor is double electric layer capacitor.
Electrolyte for capacitor provided by the invention, is made up of ionic liquid and ferrocene, and wherein the molar concentration of ferrocene is 0.001mol/L to 0.02mol/L.Ferrocene there occurs the redox reaction of high reversible in charge and discharge process, creates faraday's electric capacity, thus substantially increases the ratio capacitance of double electric layer capacitor; And ferrocene is cheaply easy to get, decomposition temperature is high, can not increase inflammable and explosive danger coefficient as organic additive; Therefore, safety of the present invention, cheaply, and can improve the specific capacity of double electric layer capacitor greatly.
Accompanying drawing explanation
Fig. 1 is the charging and discharging curve of the capacitor adopting the electrolyte in embodiment 1 to obtain.
Embodiment
A kind of electrolyte solution for electric double layer capacitor, its by ionic liquid and ferrocene or derivatives thereof (as, formyl ferrocene, acetylferrocene, methyl alcohol ferrocene or acetic acid ferrocene) hybrid reaction forms, the molar concentration of described ferrocene or its derivative is 0.001 ~ 0.02mol/L, the molar concentration of preferred ferrocene or its derivative is 0.005 ~ 0.01mol/L, and more preferably the molar concentration of ferrocene or its derivative is 0.01mol/L.
Wherein, described ionic liquid is made up of any one anion in glyoxaline cation and tetrafluoro boric acid anion, hexafluorophosphoric acid anion, two (trimethyl fluoride sulfonyl) imines anion, acetate anion, methylsulfuric acid ester anion, trifluoroacetic acid anion, trifluoromethane sulfonic acid anion, dicyanogen methyl isophorone amine anion or trifluoroacetyl fluoroform sulfonamide anions; And described glyoxaline cation is the one in 1-butyl-3-methyl imidazolium cation, 1-propyl group-3-methyl imidazolium cation, 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 (trimethyl fluoride sulfonyl) imines anion, acetate anion, methylsulfuric acid ester anion, trifluoroacetic acid anion, trifluoromethane sulfonic acid anion, dicyanogen methyl isophorone amine anion or trifluoroacetyl fluoroform sulfonamide anions; And described pyrroles's cation is the one in butyl methyl pyrroles cation, hydroxypropyl methyl pyrroles cation, ethyl-methyl pyrroles cation.
Wherein, ionic liquid is 1-butyl-3-methyl imidazolium tetrafluoroborate or butyl methyl pyrroles tetrafluoroborate.
The present invention also provides a kind of capacitor using above-mentioned electrolyte, and this capacitor is double electric layer capacitor.
Electrolyte for capacitor provided by the invention, is made up of ionic liquid and ferrocene, and wherein the molar concentration of ferrocene is 0.001mol/L to 0.02mol/L.Ferrocene there occurs the redox reaction of high reversible in charge and discharge process, creates faraday's electric capacity, thus substantially increases the ratio capacitance of double electric layer capacitor; And ferrocene is cheaply easy to get, decomposition temperature is high, can not increase inflammable and explosive danger coefficient as organic additive; Therefore, safety of the present invention, cheaply, and can improve the specific capacity of double electric layer capacitor greatly.
In the present invention, the test of specific capacity of double-layer capacitor: take Graphene as electrode material, with each embodiment for electrolyte, be assembled into button cell, utilize CHI660A electrochemical workstation to carry out constant current charge-discharge test to it, record its ratio capacitance, namely under 30 degrees celsius, in charging/discharging voltage 0-3v window ranges, after the circulation of the constant current repeated charge 50 of charging and discharging currents 1A/g, obtain its ratio capacitance; The computing formula of ratio capacitance 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, preferred embodiment of the present invention is described in further detail.
Embodiment 1
A kind of electrolyte solution for electric double layer capacitor, it is made up of 1-butyl-3-methyl imidazolium tetrafluoroborate and ferrocene, and wherein the molar concentration of ferrocene is 0.001mol/L.
Test show that the ratio capacitance of the double electric layer capacitor of electrolyte in application the present embodiment is 64F/g, than the application of pure ionic liquid recorded under equal conditions, namely to make the ratio capacitance of the double electric layer capacitor of electrolyte high by 36.7% for 1-butyl-3-methyl imidazolium tetrafluoroborate.
Fig. 1 is the charging and discharging curve of the capacitor adopting the electrolyte in embodiment 1 to obtain; Wherein, charging/discharging voltage 0-3v, charging and discharging currents 1A/g; Chain-dotted line is the electrolyte of the present embodiment, and solid line is pure ionic liquid.
Can calculate from the charging and discharging curve of Fig. 1: the ratio capacitance that application the present embodiment makes the double electric layer capacitor of electrolyte is 64F/g, and application of pure ionic liquid, namely 1-butyl-3-methyl imidazolium tetrafluoroborate makes the ratio capacitance of the double electric layer capacitor of electrolyte is 46.8F/g, test draws the ratio capacitance of the double electric layer capacitor of electrolyte in application the present embodiment, than the application of pure ionic liquid recorded under equal conditions, namely 1-butyl-3-methyl imidazolium tetrafluoroborate is high by 36.7% as the ratio capacitance of the double electric layer capacitor of electrolyte.
Embodiment 2 ~ 56 is shown in following list:
Note: in table,
1, ratio capacitance exceeds ratio is in corresponding embodiment, and the application of pure ionic liquid recorded under the ratio capacitance applying the double electric layer capacitor of electrolyte in corresponding embodiment exceeds equal conditions is as the percentage of the ratio capacitance of the double electric layer capacitor of electrolyte;
2, in embodiment 2 ~ 56, various preparation technology's flow process is identical with embodiment 1 with test condition.
Should be understood that, the above-mentioned statement for present pre-ferred embodiments is comparatively detailed, and therefore can not 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 claims.
Claims (3)
1. a double electric layer capacitor electrolytic solution, it is characterized in that, this electrolyte comprises ionic liquid and ferrocene derivatives, the molar concentration of described ferrocene derivatives is 0.005 ~ 0.01mol/L, and described ferrocene derivatives is formyl ferrocene, acetylferrocene, methyl alcohol ferrocene or acetic acid ferrocene;
Ionic liquid is the ionic liquid that any one anion in pyrroles's cation and tetrafluoro boric acid anion, hexafluorophosphoric acid anion, two (trimethyl fluoride sulfonyl) imines anion, acetate anion, methylsulfuric acid ester anion, trifluoroacetic acid anion, trifluoromethane sulfonic acid anion, dicyanogen methyl isophorone amine anion and trifluoroacetyl fluoroform sulfonamide anions forms;
Described pyrroles's cation is any one in butyl methyl pyrroles cation, hydroxypropyl methyl pyrroles cation or ethyl-methyl pyrroles cation.
2. double electric layer capacitor electrolytic solution according to claim 1, is characterized in that, described ionic liquid is butyl methyl pyrroles tetrafluoroborate.
3. a double electric layer capacitor, is characterized in that, this capacitor comprises the arbitrary described electrolyte of claim 1 to 2.
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