CN102956363A - Electrolyte and double-electric-layer capacitor - Google Patents
Electrolyte and double-electric-layer capacitor Download PDFInfo
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- CN102956363A CN102956363A CN2011102362395A CN201110236239A CN102956363A CN 102956363 A CN102956363 A CN 102956363A CN 2011102362395 A CN2011102362395 A CN 2011102362395A CN 201110236239 A CN201110236239 A CN 201110236239A CN 102956363 A CN102956363 A CN 102956363A
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- cation
- electrolyte
- ionic liquid
- layer capacitor
- electrolyte according
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 39
- 239000003990 capacitor Substances 0.000 title claims abstract description 27
- -1 hexafluorophosphate Chemical compound 0.000 claims abstract description 48
- 239000002608 ionic liquid Substances 0.000 claims abstract description 22
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 6
- 241000790917 Dioxys <bee> Species 0.000 claims description 4
- 229910000085 borane Inorganic materials 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 150000004714 phosphonium salts Chemical class 0.000 claims description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 4
- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 claims description 2
- GNKNSMZARWPXLO-UHFFFAOYSA-N C(CCCCC)C=1[C+]=NC=CC1 Chemical compound C(CCCCC)C=1[C+]=NC=CC1 GNKNSMZARWPXLO-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 125000005605 benzo group Chemical group 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000003233 pyrroles Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 238000010494 dissociation reaction Methods 0.000 abstract description 2
- 230000005593 dissociations Effects 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract 5
- 230000005518 electrochemistry Effects 0.000 abstract 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 4
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 4
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- 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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- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention belongs to the field of electrochemistry and discloses electrolyte and a double-electric-layer capacitor. The electrolyte comprises hexafluorophosphate ionic liquid and fluorinated alkyl boride in the molar ratio of 1:0.001-1:0.05. The electrolyte for the double-electric-layer capacitor is obtained by mixing the hexafluorophosphate ionic liquid with the fluorinated alkyl boride, and the fluorinated alkyl boride and PF6- can form a complex, so that the dissociation degree of the hexafluorophosphate ionic liquid is increased, conductivity of the electrolyte is increased greatly, and equivalent internal resistance of the double-electric-layer capacitor is lowered greatly. The fluorinated alkyl boride is used as additives, the conductivity of the electrolyte is increased greatly only with the fluorinated alkyl boride accounting for not more than 5% of the total mass of the electrolyte, and if organic solvents are added to increase the conductivity, a great amount of organic liquid is needed to dissolve the hexafluorophosphate ionic liquid low in dissolvability, so that consumption cost of the electrolyte is saved greatly.
Description
Technical field
The present invention relates to electrochemical field, relate in particular to a kind of electrolyte.This invention also relates to a kind of double electric layer capacitor that uses 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 of military field, device for mobile communication, computer and electric automobile etc.As the important component part of double electric layer capacitor, electrolyte has a significant impact 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 that is comprised 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 the appearance of ionic liquid greatly.The advantages such as it has that conductivity is high, electrochemical window is wide, non-volatile, not flammable, Heat stability is good.Ionic liquid has good development prospect as the electrolyte of double electric layer capacitor, yet pure ionic liquid capacitance at ambient temperature is not high, causes the equivalent internal resistance of the double electric layer capacitor that uses pure ionic liquid to do electrolyte bigger than normal.Hexafluoro phosphonates ionic liquid because easily synthetic, cost is low, it is one of at present the most frequently used il electrolyte, but because resistance is high, and limited its application as electrolyte solution for electric double layer capacitor, adopt the way of adding a large amount of organic solvents (acetonitrile, propene carbonate, 1-butyrolactone) can reach the purpose that greatly reduces the double electric layer capacitor equivalent internal resistance, the consumption of double electric layer capacitor electrolyte is increased greatly, thereby increase cost.
Summary of the invention
The object of the present invention is to provide a kind of cost low, and can reduce the electrolyte of capacitor equivalent internal resistance.
A kind of electrolyte comprises hexafluoro phosphonates ionic liquid and fluoro-alkyl boride, and the mol ratio of described hexafluoro phosphonates ionic liquid and fluoro-alkyl boride is 1: 0.001～1: 0.05; Preferably, the mol ratio of described hexafluoro phosphonates ionic liquid and fluoro-alkyl boride is 1: 0.01～1: 0.05.
In the above-mentioned electrolyte, in the described hexafluoro phosphonates ionic liquid, cation is selected from imidazole salt cation, quaternary ammonium salts cation, pyrroles's salt cationoid, season phosphonium salt cationoid or pyridiniujm cationoid, and anion is the hexafluorophosphoric acid anion; Wherein:
Described imidazole salt cation is selected from 1-butyl-3-methylimidazole cation, 1-propyl group-3-methylimidazole cation or 1-ethyl-3-methylimidazole cation;
Described quaternary ammonium salts cation is selected from methyl triethyl group quaternary ammonium cation, tetraethyl quaternary ammonium cation or trimethyl propyl group quaternary ammonium cation;
Described pyroles cation is selected from butyl methyl pyrroles cation, propyl group methylpyrrole cation or ethyl-methyl pyrroles cation;
Described season the phosphonium salt cationoid be selected from trimethyl hexyl season phosphine cation, triethyl group hexyl season phosphine cation or tri-methyl-amyl season the phosphine cation;
Described pyridiniujm cationoid is selected from butyl-pyridinium cation, pentyl pyridine cation or hexyl pyridylium.
In the above-mentioned electrolyte, described fluoro-alkyl boride is selected from 2-difluoro-benzene base-phenyl-monofluoride and dioxy borine (i.e. (C
6H
3F) O
2B (C
6H
3F
2)) or 2-perfluorophenyl-tetrafluoro benzo dioxy borine (i.e. (C
6F
4) O
2B (C
6F
5)).
Another object of the present invention is to provide a kind of double electric layer capacitor, this double electric layer capacitor uses above-mentioned electrolyte provided by the invention
The invention provides a kind of electrolyte solution for electric double layer capacitor, it is mixed by hexafluoro phosphonates ionic liquid and fluoro-alkyl boride; And fluoro-alkyl boride energy and PF
6 -(being hexafluoro phosphonic acids anion) forms complex, thereby the degree of dissociation of hexafluoro phosphonates ionic liquid is increased, thereby increases substantially its conductivity, greatly reduces the equivalent internal resistance of double electric layer capacitor; And the fluoro-alkyl boride is to use as additive, only need 5% of gross mass just can reach the effect that increases substantially its conductivity with interior, to need a large amount of organic liquids to make the low hexafluoro phosphonates ion liquid dissolving of solubility and improve conductivity by the interpolation organic solvent, greatly save the consumption cost of electrolyte.
Description of drawings
The ac impedance spectroscopy of the capacitor that Fig. 1 makes for the electrolyte that adopts among the embodiment 1.
Embodiment
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
In glove box, be 1: 0.05 1-butyl-3-methylimidazole hexafluoro phosphonate and (C with mol ratio
6H
3F) O
2B (C
6H
3F
2) mix, stir after 20 minutes (C
6H
3F) O
2B (C
6H
3F
2) be dissolved in 1-butyl-3-methylimidazole hexafluoro phosphonate; At this moment, obtain a kind of electrolyte solution for electric double layer capacitor, namely contain (C
6H
3F) O
2B (C
6H
3F
2) 1-butyl-3-methylimidazole hexafluoro phosphonate electrolyte.
In the present embodiment, the test of equivalent internal resistance: take Graphene as electrode material, take each embodiment as electrolyte, be assembled into capacitor, be button cell in the present embodiment, utilize the CHI660A electrochemical workstation that it is carried out ac impedance measurement, its equivalent internal resistance is directly read by section from ac impedance spectroscopy.
The ac impedance spectroscopy of the capacitor that Fig. 1 makes for the electrolyte that adopts among the embodiment 1; Wherein, abscissa is real part, and ordinate is imaginary part (AC impedance is measured the data of coming and processed the plural number that draws for the process Mathematical Modeling, and ac impedance spectroscopy is complex number plane figure, and real part and imaginary part be real part and the imaginary part of corresponding Mathematical Modeling respectively); As can be seen from Figure 1, the equivalent internal resistance of the embodiment of the invention 1 is 22 Ω, and the equivalent internal resistance of pure ionic liquid is 70 Ω, and the equivalent internal resistance of the embodiment of the invention 1 is than the equivalent internal resistance low 68.6% of the pure ionic liquid 1-butyl-3-methyl imidazolium hexafluoro phosphonate electrolyte that records under the equal conditions.
Embodiment 2～24 sees following table 1
Claims (10)
1. an electrolyte is characterized in that, this electrolyte comprises hexafluoro phosphonates ionic liquid and fluoro-alkyl boride, and the mol ratio of described hexafluoro phosphonates ionic liquid and fluoro-alkyl boride is 1: 0.001～1: 0.05.
2. electrolyte according to claim 1 is characterized in that, the mol ratio of described hexafluoro phosphonates ionic liquid and fluoro-alkyl boride is 1: 0.01～1: 0.05.
3. electrolyte according to claim 1 and 2, it is characterized in that, in the described hexafluoro phosphonates ionic liquid, cation is selected from imidazole salt cation, quaternary ammonium salts cation, pyrroles's salt cationoid, season phosphonium salt cationoid or pyridiniujm cationoid, and anion is the hexafluorophosphoric acid anion.
4. electrolyte according to claim 3 is characterized in that, described imidazole salt cation is selected from 1-butyl-3-methylimidazole cation, 1-propyl group-3-methylimidazole cation or 1-ethyl-3-methylimidazole cation.
5. electrolyte according to claim 3 is characterized in that, described quaternary ammonium salts cation is selected from methyl triethyl group quaternary ammonium cation, tetraethyl quaternary ammonium cation or trimethyl propyl group quaternary ammonium cation.
6. electrolyte according to claim 3 is characterized in that, described pyroles cation is selected from butyl methyl pyrroles cation, propyl group methylpyrrole cation or ethyl-methyl pyrroles cation.
7. electrolyte according to claim 3 is characterized in that, described season the phosphonium salt cationoid be selected from trimethyl hexyl season phosphine cation, triethyl group hexyl season phosphine cation or tri-methyl-amyl season the phosphine cation.
8. electrolyte according to claim 3 is characterized in that, described pyridiniujm cationoid is selected from butyl-pyridinium cation, pentyl pyridine cation or hexyl pyridylium.
9. electrolyte according to claim 1 and 2 is characterized in that, described fluoro-alkyl boride is selected from 2-difluoro-benzene base-phenyl-monofluoride and dioxy borine or 2-perfluorophenyl-tetrafluoro benzo dioxy borine.
10. a double electric layer capacitor is characterized in that, this double electric layer capacitor right to use requires 1 described electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102362395A CN102956363A (en) | 2011-08-17 | 2011-08-17 | Electrolyte and double-electric-layer capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102362395A CN102956363A (en) | 2011-08-17 | 2011-08-17 | Electrolyte and double-electric-layer capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102956363A true CN102956363A (en) | 2013-03-06 |
Family
ID=47765056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102362395A Pending CN102956363A (en) | 2011-08-17 | 2011-08-17 | Electrolyte and double-electric-layer capacitor |
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| CN (1) | CN102956363A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113632282A (en) * | 2019-03-29 | 2021-11-09 | 株式会社村田制作所 | Electrolyte for secondary battery and secondary battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6352798B1 (en) * | 1997-12-08 | 2002-03-05 | Brookhaven Science Associates, Llc | Phenyl boron-based compounds as anion receptors for non-aqueous battery electrolytes |
| CN101228602A (en) * | 2005-07-29 | 2008-07-23 | 广荣化学工业株式会社 | Electrochemical device |
| CN101271989A (en) * | 2008-04-30 | 2008-09-24 | 深圳新宙邦科技股份有限公司 | Lithium-ion battery room temperature ionic liquid electrolyte and preparation method thereof |
-
2011
- 2011-08-17 CN CN2011102362395A patent/CN102956363A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6352798B1 (en) * | 1997-12-08 | 2002-03-05 | Brookhaven Science Associates, Llc | Phenyl boron-based compounds as anion receptors for non-aqueous battery electrolytes |
| CN101228602A (en) * | 2005-07-29 | 2008-07-23 | 广荣化学工业株式会社 | Electrochemical device |
| CN101271989A (en) * | 2008-04-30 | 2008-09-24 | 深圳新宙邦科技股份有限公司 | Lithium-ion battery room temperature ionic liquid electrolyte and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 黄倩: ""锂离子电池的热效应及其安全性能的研究"", 《中国博士学位论文全文数据库 工程科技Ⅱ辑》, 15 December 2007 (2007-12-15) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113632282A (en) * | 2019-03-29 | 2021-11-09 | 株式会社村田制作所 | Electrolyte for secondary battery and secondary battery |
| CN113632282B (en) * | 2019-03-29 | 2023-10-03 | 株式会社村田制作所 | Electrolyte for secondary battery and secondary battery |
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| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
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Application publication date: 20130306 |