CN100466370C - An electrolyte for super capacitance cell - Google Patents
An electrolyte for super capacitance cell Download PDFInfo
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- CN100466370C CN100466370C CNB2007100352068A CN200710035206A CN100466370C CN 100466370 C CN100466370 C CN 100466370C CN B2007100352068 A CNB2007100352068 A CN B2007100352068A CN 200710035206 A CN200710035206 A CN 200710035206A CN 100466370 C CN100466370 C CN 100466370C
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- Prior art keywords
- electrolyte
- carbonate
- ester
- organic solvent
- super capacitance
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- Y02E60/122—
Abstract
The invention discloses an electrolyte to prepare hyper capacitance battery, which comprises the following parts: lithium salt, non-water organic solvent and additive, wherein the non-water organic solvent is at least two parts of dimethyl carbonate, diethyl carbonate, propylene carbonate ester, ethyl carbonate ester, sulfite vinyl ester, sulfite propone ester, butane ester carbonate, Y-butyrolactone, methyl vinyl carbonate, methyl propyl ester carbonate, acetic ester and acetonitrile. The invention is compatible with capacitance and battery, which possesses high-power density, large current discharge and good circulating life.
Description
Technical field
The present invention relates to the electrolyte that a kind of electrochemical energy storing device is used, especially relate to a kind of electrolyte for super capacitance cell.
Background technology
The super capacitance cell system is a kind of ultracapacitor is combined with secondary cell (being mainly lithium ion battery at present) and the novel green energy-storage system that is expected to have concurrently both advantages that constitutes.In the super capacitance cell system, the combination of these two kinds of energy storage systems of ultracapacitor and secondary cell has two kinds, and a kind of is " outer combination " formula (monomer that is about to both is combined into an energy storage component or system by power-supply management system); Another kind is " interior combination " formula (being about to both organically is combined in the same monomer).Based on ultracapacitor interfacial electric double layer and lithium ion battery embedding-Tuo embedding two aspect characteristics novel energy-storing device---super capacitance cell, it has the characteristics of electric capacity and the difunctional energy storage of battery concurrently, when keeping lithium ion battery high voltage, high-energy-density, also have the high power density, heavy-current discharge of ultracapacitor, the characteristics of good cycle life.There are some researches show, constitute super capacitance cell with lithium ion battery by " the interior combination ", be expected to obtain excellent more performance by ultracapacitor based on active carbon electrode material.Xia Yongyao has proposed a kind of mixed type watersoluble lithium ion battery that lithium ion embedding-Tuo embedding mechanism and electrochemical capacitor electric double layer mechanism coordination are combined in 2005 (CN1674347), adopts to contain Li
+The aqueous solution make electrolyte.In the aqueous solution, the voltage of the battery of its report is lower, is difficult to compete mutually with existing lithium ion battery.
Mainly be to adopt EC, DMC etc. in simple lithium ion battery for solvent, with LiPF
6Deng lithium salts is solute, adds suitable additives and constitutes electrolyte, the Li in the electrolyte
+For the work ion, in charge and discharge process, play the effect that embeds-take off embedding, and Li
+It also is the material that forms the SEI film in battery cathode.But the electrolytic conductivity of existing lithium ion battery is relatively low.For being the ultracapacitor that electrode material carries out the electric double layer energy storage with the active carbon, need to have in the electrolyte enough ions to form electric double layer with activated carbon surface in when charging and come the generation capacity, certain electrolyte that also requires has conductivity height, characteristic that decomposition voltage is high.But, existing lithium salts such as LiPF
6Solubility is not high in the solvent of capacitor electrolyte, and the effects of ion number is few, causes conductivity lower.That is to say that the energy storage principle of ultracapacitor and lithium ion battery is distinguishing, when with lithium ion battery and monomer of ultracapacitor composition, electrolyte must satisfy the requirement of two kinds of different operating principles simultaneously.Simultaneously, also require electrolyte to have the characteristic of high conductivity, broad potential window, thereby make super capacitance cell have the characteristics of high-energy-density and high power density.
Summary of the invention
The objective of the invention is to propose a kind of when satisfying lithium ion battery and ultracapacitor and forming a monomer, the requirement of two kinds of different operating principles has the characteristic of high conductivity, broad potential window, a kind of electrolyte for super capacitance cell.
Purpose of the present invention realizes by following manner:
Electrolyte comprises lithium salts, non-aqueous organic solvent, additive; Described non-aqueous organic solvent is at least two kinds in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate, ethylene sulfite, propylene sulfite, butylene, gamma-butyrolacton, methyl ethyl carbonate alkene ester, carbonic acid first propyl ester, ethyl acetate, the acetonitrile.
Ethylene carbonate content is not more than 40% in the preferred mixed liquor of described non-aqueous organic solvent, the propylene carbonate ester content is not more than 30%, and ethane nitrile content is not more than 30%, and carbonic acid first propyl ester is not more than 40%, dimethyl carbonate is not more than 50%, and diethyl carbonate is not more than 40% mixed liquor; Account for the weight of electrolyte in each composition.
Described lithium salts is LiPF
6, LiBF
4, LiBOB, LiCF
3SO
3, LiN (SO
2CF
3)
2, LiC (SO
2CF
3)
3, LiAsF
6In at least a, addition is 8-18%.
Electrolyte also comprises ammonium salt.It is 5-40% that ammonium salt accounts for electrolyte weight content.
Described ammonium salt is Et
4NBF
4, Et
4NPF
6, Et
4NClO
4, MeEt
3NBF
4, Me
3EtNBF
4, Et
4NCF
3SO
3, Et
4NCF
3SO
3, Et
4N (CF
3SO
2)
2At least a among the N.Additive comprises that small molecule amine class or ethers are at least a, accounts for the 0.2-5% of electrolyte weight.
Additive can be methylamine, ethamine, acetamide or formamide.
Electrolyte of the present invention comprises non-aqueous organic solvent and electrolytic salt.It optionally proposes to adopt and contains Li
+Electrolyte, adopt carbonates solvent and functional additive, synthetic electrolyte comprises Li thereby improve
+Electrolyte ion in the migration rate of electrolyte and electrode interface, thereby when making super capacitance cell have high-energy-density, also have high power density, heavy-current discharge, the characteristics in good circulation life-span.
Electrolyte for super capacitance cell of the present invention is to use on the basis of electrolyte at single lithium ion battery and single ultracapacitor, based on the electrolyte of lithium salts electrolyte, optionally adds ammonium salt, selects the appropriate organic solvent system; Simultaneously, selectivity adds functional additive, makes the conductivity of electrolyte than the conductivity of lithium ion battery raising be arranged, thereby satisfies the requirement of super capacitance cell.All about 10mS/cm, the multiplying power property of battery and cycle performance are not good for the conductivity of business-like electrolyte for lithium ion battery on the existing market.The present invention on the basis in conjunction with lithium-ion battery electrolytes and electrolytic solution for super capacitor, selects novel electrolyte and dicyandiamide solution; And the employing new additive agent, improve lithium ion to the contribution rate of conductivity with improve the migration rate of electrolyte ion in electrolyte and interface, make the conductivity of electrolyte reach 15-25mS/cm, satisfy the requirement of super capacitance cell.
Advantage of the present invention is to select appropriate solvent to form and functional additive, improves lithium salts and degree of dissociation and the mobility of ammonium salt in solution, thereby makes super capacitance cell have high power density, energy density and long cycle life.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but these embodiment must not be interpreted as limiting the scope of the invention.
Embodiment 1
At normal temperature and pressure moisture is 3ppm, and under the environment of inert gas, with purity all at the solvent more than 99.95%, 10% propene carbonate, 21% ethylene carbonate, 29.5% dimethyl carbonate, 10% methyl ethyl carbonate mixes, dissolving 16% lithium salts LiPF in this mixed solvent
6, 12.5% Et
4NBF
4, average mark adds for four times, and each time interval 2h that adds fully shakes up after the adding, adds 1.0% acetamide at last.Be configured to electrolyte.
Adopt business-like spinelle LiMn
2O
4And active carbon, take by weighing LiMn by weight 3:7
2O
4Mix as positive electrode active materials with active carbon.The anodal batching by active material: the weight ratio of carbon black: binding agent=80:12:8 is carried out mixed slurry, evenly is coated on the aluminum foil current collector that thickness is 25 μ m, dries at 120 ℃ and makes electrode.Adopt business-like Delanium and active carbon to mix as negative active core-shell material.Cathode blending is by active material: the weight ratio of carbon black: binding agent=86:8:6 is carried out mixed slurry, and evenly being coated on thickness is on the Copper Foil collector of 15 μ m, dries at 120 ℃ and makes electrode.Then these two kinds of electrodes are cut according to specification, matched group is dressed up 204468 batteries, and the barrier film that is adopted is commercial lithium ion battery separator.
Detection method:, measure the conductivity of electrolyte with conductivity meter with the moisture in the DL32 karl Fischer coulometry moisture titrator mensuration electrolyte.Record moisture 6ppm, conductivity 16mS/cm.
Work in the 2.2-4.0V voltage range, discharging current electric current 1C capacity is 4Ah.The 10C charge/discharge capacity maintains 3.7Ah, after 2000 circulations, and capability retention〉90%.
Embodiment 2
10% propene carbonate, 10.5% ethylene carbonate, 32% dimethyl carbonate, 10% methyl ethyl carbonate mixes, dissolving 16% lithium salts LiPF in this mixed solvent
6, 20% MeEt
3NBF
4, 1.5% acetamide, all the other are with embodiment 1.Record moisture 6ppm, conductivity 17mS/cm.
Work in the 2.2-4.0V voltage range, discharging current 1C capacity is 4Ah.The 10C charge/discharge capacity maintains 3.7Ah, after 2000 circulations, and capability retention〉90%.
Embodiment 3
23% acetonitrile, 10.5% ethylene carbonate, 24.5% dimethyl carbonate, 6% methyl ethyl carbonate mixes, dissolving 10% lithium salts LiPF in this mixed solvent
6, 24%MeEt
3NBF
4, 2% acetamide all the other with embodiment 1.Record moisture 6ppm, conductivity 25mS/cm.
Work in the 2.2-4.0V voltage range, discharging current 1C capacity is 4Ah.The 10C charge/discharge capacity maintains 3.9Ah, after 2000 circulations, and capability retention〉93%.
Embodiment 4
20% acetonitrile, 12.5% ethylene carbonate, 26.5% dimethyl carbonate, 6% methyl ethyl carbonate mixes, dissolving 10% lithium salts LiPF in this mixed solvent
6, 11.5% MeEt
3NBF
4, 12.5% Et
4NBF
4, all the other are with embodiment 1.Record moisture 6ppm, conductivity 21mS/cm.
Work in the 2.2-4.0V voltage range, discharging current 1C capacity is 4Ah.The 10C charge/discharge capacity maintains 3.8Ah, after 2000 circulations, and capability retention〉92%.
Embodiment 5
30% acetonitrile, 30% ethylene carbonate, dissolving 16.5% lithium salts LiPF in this mixed solvent
6, 22%MeEt
3NBF
4, adding 1.5% formamide at last, all the other are with embodiment 1.Record moisture 8ppm, conductivity 23mS/cm.
Work in the 2.2-4.0V voltage range, discharging current 1C capacity is 4Ah.The 10C charge/discharge capacity maintains 3.8Ah, after 2000 circulations, and capability retention〉90%.
Embodiment 6
30% acetonitrile, 20% ethylene carbonate, dissolving 12% lithium salts LiPF in this mixed solvent
6, 20%MeEt
3NBF
4, 15% Et
4NBF
4, adding 3% formamide at last, all the other are with embodiment 1.Record moisture 6ppm, conductivity 21mS/cm.
Work in the 2.2-4.0V voltage range, discharging current electric current 1C capacity is 4Ah.The 10C charge/discharge capacity maintains 3.7Ah, after 2000 circulations, and capability retention〉90%.
Claims (3)
1. one kind prepares the electrolyte that super capacitance cell is used, and it is characterized in that: electrolyte comprises lithium salts, non-aqueous organic solvent, additive and ammonium salt; Described non-aqueous organic solvent is at least two kinds in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate, ethylene sulfite, propylene sulfite, butylene, gamma-butyrolacton, methyl ethyl carbonate alkene ester, carbonic acid first propyl ester, ethyl acetate, the acetonitrile;
Account for the weight of electrolyte in each composition: ethylene carbonate content is not more than 40% in the mixed liquor of non-aqueous organic solvent, the propylene carbonate ester content is not more than 30%, ethane nitrile content is not more than 30%, carbonic acid first propyl ester is not more than 40%, dimethyl carbonate is not more than 50%, and diethyl carbonate is not more than 40%;
Described lithium salts is LiPF
6, LiBF
4, LiBOB, LiCF
3SO
3, LiN (SO
2CF
3)
2, LiC (SO
2CF
3)
3, LiAsF
6In at least a, the weight content that described lithium salts accounts for electrolyte is 8-18%;
Described ammonium salt accounts for the weight content 5-40% of electrolyte;
Described ammonium salt is Et
4NBF
4, Et
4NPF
6, Et
4NClO
4, MeEt
3NBF
4, Me
3EtNBF
4, Et
4NCF
3SO
3, Et
4NCF
3SO
3, Et
4N (CF
3SO
2)
2At least a among the N.
2, a kind of electrolyte that super capacitance cell is used for preparing according to claim 1, it is characterized in that: additive comprises small molecule amine or ether, accounts for the 0.2-5% of electrolyte weight.
3, a kind of electrolyte that super capacitance cell is used for preparing according to claim 2, it is characterized in that: additive is methylamine, ethamine, acetamide or formamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100352068A CN100466370C (en) | 2007-06-25 | 2007-06-25 | An electrolyte for super capacitance cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100352068A CN100466370C (en) | 2007-06-25 | 2007-06-25 | An electrolyte for super capacitance cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101079511A CN101079511A (en) | 2007-11-28 |
| CN100466370C true CN100466370C (en) | 2009-03-04 |
Family
ID=38906820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100352068A Expired - Fee Related CN100466370C (en) | 2007-06-25 | 2007-06-25 | An electrolyte for super capacitance cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100466370C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102780037B (en) * | 2012-07-19 | 2017-07-28 | 宁德新能源科技有限公司 | A kind of nonaqueous electrolyte and the lithium ion battery comprising the nonaqueous electrolyte |
| CN103943376A (en) * | 2013-01-22 | 2014-07-23 | 中国科学院大连化学物理研究所 | Electrolyte of mixed type super capacitor |
| KR102379565B1 (en) | 2014-12-22 | 2022-03-29 | 삼성에스디아이 주식회사 | Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery comprising the same |
| CN107275120A (en) * | 2017-07-25 | 2017-10-20 | 陕西科技大学 | A kind of electrolysis additive and its application in lithium ion hydridization ultracapacitor |
| CN110517901B (en) * | 2019-09-20 | 2021-09-07 | 合肥工业大学 | Wide-temperature-area electrolyte for super capacitor and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07142090A (en) * | 1993-11-18 | 1995-06-02 | Yoshiharu Matsuda | Lithium secondary battery electrolyte containing additive |
| CN1495957A (en) * | 2002-09-12 | 2004-05-12 | ����Sdi��ʽ���� | Electrolyte for lithium secondary battery and lithium secondary battery containing the same |
| WO2006080204A1 (en) * | 2005-01-26 | 2006-08-03 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous electrolyte and secondary battery containing same |
| CN1925207A (en) * | 2006-09-20 | 2007-03-07 | 广州市天赐高新材料科技有限公司 | High rate electrolyte for lithium ion battery |
-
2007
- 2007-06-25 CN CNB2007100352068A patent/CN100466370C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07142090A (en) * | 1993-11-18 | 1995-06-02 | Yoshiharu Matsuda | Lithium secondary battery electrolyte containing additive |
| CN1495957A (en) * | 2002-09-12 | 2004-05-12 | ����Sdi��ʽ���� | Electrolyte for lithium secondary battery and lithium secondary battery containing the same |
| WO2006080204A1 (en) * | 2005-01-26 | 2006-08-03 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous electrolyte and secondary battery containing same |
| CN1925207A (en) * | 2006-09-20 | 2007-03-07 | 广州市天赐高新材料科技有限公司 | High rate electrolyte for lithium ion battery |
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| Publication number | Publication date |
|---|---|
| CN101079511A (en) | 2007-11-28 |
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Granted publication date: 20090304 Termination date: 20190625 |