CN1385918A - Novel electrolyte for lithium ion cell - Google Patents
Novel electrolyte for lithium ion cell Download PDFInfo
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- CN1385918A CN1385918A CN02109812A CN02109812A CN1385918A CN 1385918 A CN1385918 A CN 1385918A CN 02109812 A CN02109812 A CN 02109812A CN 02109812 A CN02109812 A CN 02109812A CN 1385918 A CN1385918 A CN 1385918A
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- lithium ion
- electrolyte
- ion battery
- novel electrolyte
- biphenyl
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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
- Y02E60/10—Energy storage using batteries
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Abstract
A new type electrolyte used in lithium ionic battery relates to solving the problem of insecurity due to overcharge of lithium ionic battery by adding monomer addition agent of high activated polymer in the existing electrolyte lithium ionic batteries in which the quality percent consentration is 3-10% of the new type electrolyte of the pyridine class substance biphenyl class or carbazole class matters or their mixtures. The said pyridine class matter is 2-vinylpyridine, 4-vinylpyridine and the biphenyl substance is 2-biphenyl or 3-biphenyl and carbazole matter is N-vinylcarbazole. This invention can guarantee the lithium ionic battery to changed constantly at 12V. without weeping, smoking, catching five or explosion.
Description
Technical field: the present invention relates to a kind of electrolyte, particularly can solve the lithium ion battery electrolyte of unsafe problems that overcharges.
Background technology: lithium ion battery is novel chemical power source, have energy density height, operating voltage height, characteristics such as load characteristic is good, charging rate is fast, have extended cycle life, safety non-pollution, be widely used in fields such as mobile phone, notebook computer, palmtop PC at present.But this battery also exists a more serious technical problem, promptly under charging voltage too high (more than or equal to 4.8 volts) situation, leakage can take place in battery, smolder even phenomenon such as exploding and firing, bring hidden danger for user's use, also directly have influence on the application of lithium ion battery in the high reliability system simultaneously.
Summary of the invention: the present invention is a kind of electrolyte that is used for lithium ion battery of development.This electrolyte has solved lithium ion battery under high overcharge voltage, leakage easily takes place, smolders, unsafe problems such as exploding and firing.The present invention is the made novel electrolyte of additive that adds the highly reactive polymer monomer in the electrolyte of existing lithium ion battery, and the mass percent concentration of highly reactive polymer monomeric additive is 3～10% in the novel electrolyte.Described highly reactive polymer monomeric additive is pyridines material, biphenyl class material or carbazoles material, or their mixture.Described pyridines material is 2-vinylpyridine or 4-vinylpridine; Described biphenyl class material is biphenyl or terphenyl; Described carbazoles material is the N-vinylcarbazole.The characteristics of above-mentioned highly reactive polymer monomer are more stable at normal temperatures, and temperature can rapid polymerization after raising.Electrolyte in the above-mentioned existing lithium ion battery is to adopt lithium salts to be dissolved in the organic solvent to make, and the concentration of lithium salts in organic solvent is 0.75～1.25mol/L, and described lithium salts is: LiPF
6, LiBF
4, LiAsF
6Or LiClO
4, described organic solvent is binary or the ternary organic solvent that propylene carbonate or ethylene carbonate and oxolane, dimethyl carbonate, diethyl carbonate, Methylethyl carbonic ester are formed.The basic principle of highly reactive polymer monomeric additive is: battery is under normal charge status, and additive generally can also improve the capacity of battery to the work and the not influence of performance of battery; When battery overcharge, an electric energy part is converted into heat energy, temperature in the battery can raise, this moment, additive therefor at a certain temperature can rapid polymerization, the internal resistance of cell is improved rapidly, and the electric current by battery drops to very little value fast, even approaches zero, thereby avoided the thermal decomposition of electrolyte and the rising of inner pressure of battery and temperature, thoroughly solved the unsafe problems of overcharging of lithium ion battery.The present invention can guarantee lithium ion battery constant voltage charge under 12 volts of voltages, and leakage can not appear in battery, the phenomenon of blast of smoldering, catch fire.
Description of drawings: Fig. 1 is to use the lithium ion battery of the existing electrolyte curve chart that overcharges, and Fig. 2 is the lithium ion battery of the using novel electrolyte of the present invention curve chart that overcharges.Curve a is the electric current change curve among the figure, and curve b is the change in voltage curve.
Embodiment one: the novel electrolyte of present embodiment is made up of electrolyte in the existing lithium ion battery and highly reactive polymer monomeric additive, and the mass percent concentration of highly reactive polymer monomeric additive is 3～5% in the novel electrolyte.The high polymer monomeric additive adopts the 2-vinylpyridine in the pyridines material.Electrolyte in the above-mentioned existing lithium ion battery is to adopt inorganic lithium salt to be dissolved in the organic solvent to make, and the concentration of inorganic lithium salt in organic solvent is 1 mole of inorganic salts of dissolving in every liter of solvent.Used inorganic lithium salt is lithium hexafluoro phosphate (LiPF
6).Organic solvent adopts the mixture of ethylene carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC), and the mol ratio of three kinds of materials is EC: DMC: DEC=4: 3: 3.The technological process of production of lithium ion battery is: the electric core of pole piece production → roll up → go into shell seals → and fluid injection → chemical examination, detects.Above-mentioned highly reactive polymer monomeric additive is to preserve down at-10 ℃～-20 ℃.Above-mentioned novel electrolyte is under-60 ℃～60 ℃ conditions the electrolysis liquid phase of highly reactive polymer monomeric additive and existing lithium ion battery to be mixed and made into, and novel electrolyte is to charge in the battery in the fluid injection process in back 2 hours in mixing.
Embodiment two: what present embodiment and embodiment one were different is: the mass percent concentration of highly reactive polymer monomeric additive is 5～7% in the novel electrolyte.Other composition, technical process and condition are identical with embodiment one.
Embodiment three: what present embodiment and embodiment one were different is: the mass percent concentration of highly reactive polymer monomeric additive is 7～10% in the novel electrolyte.Other composition, technical process and condition are identical with embodiment one, two.
Embodiment four: what present embodiment and embodiment one, two, three were different is: the high polymer monomeric additive adopts the biphenyl in the biphenyl class material.Other composition, technical process and condition are identical with embodiment one, two, three.
Embodiment five: what present embodiment and embodiment one, two, three were different is: the high polymer monomeric additive adopts the N-vinylcarbazole in the carbazoles material.Other composition, technical process and condition are identical with embodiment one, two, three.
Embodiment six: what present embodiment and embodiment one, two, three, four, five were different is: organic solvent adopts the mixture of ethylene carbonate (EC), dimethyl carbonate (DMC) and Methylethyl carbonic ester (EMC), and the mol ratio of three kinds of materials is EC: DMC: EMC=4: 3: 3.Other composition, technical process and condition are identical with embodiment one, two, three, four, five.
Embodiment seven: what present embodiment and embodiment one, two, three, four, five were different is: organic solvent adopts the mixture of ethylene carbonate (EC), dimethyl carbonate (DMC) and Methylethyl carbonic ester (EMC), and the mol ratio of three kinds of materials is EC: DMC: EMC=3: 3: 4.Other composition, technical process and condition are identical with embodiment one, two, three, four, five.
The comparative test:
1, to the test of overcharging of the existing lithium ion battery before the present invention, its test result is referring to Fig. 1.
2, form novel electrolyte by lithium hexafluoro phosphate, ethylene carbonate, dimethyl carbonic ether, Methylethyl carbonic ester and biphenyl, the weight percent concentration of biphenyl in novel electrolyte is 8%.To the lithium ion battery that the adopts above-mentioned novel electrolyte test of overcharging, its test result is referring to Fig. 2.
As can be seen from the figure, before using achievement of the present invention lithium ion battery is adopted 4.8 volts constant voltages chargings, the electric current by battery descended before this, rose rapidly then, and battery temperature is fast rise also, and after the battery explosion burning, electric current is decline rapidly again; After having used achievement of the present invention, adopt 12 volts constant voltages to charge to lithium ion battery, the electric current by battery descends always, is stabilized in a very little current value at last, and battery temperature is constant substantially.
Claims (6)
1, the novel electrolyte that is used for lithium ion battery, it is characterized in that it is the made novel electrolyte of additive that adds the highly reactive polymer monomer in the electrolyte of existing lithium ion battery, the mass percent concentration of highly reactive polymer monomeric additive is 3～10% in the novel electrolyte.
2, the novel electrolyte that is used for lithium ion battery according to claim 1 is characterized in that described highly reactive polymer monomeric additive is pyridines material, biphenyl class material or carbazoles material, or their mixture.
3, the novel electrolyte that is used for lithium ion battery according to claim 2 is characterized in that described pyridines material is 2-vinylpyridine or 4-vinylpridine; Described biphenyl class material is biphenyl or terphenyl: described carbazoles material is the N-vinylcarbazole.
4, the novel electrolyte that is used for lithium ion battery according to claim 1, the mass percent concentration that it is characterized in that highly reactive polymer monomeric additive in the novel electrolyte is 3～5%.
5, the novel electrolyte that is used for lithium ion battery according to claim 1, the mass percent concentration that it is characterized in that highly reactive polymer monomeric additive in the novel electrolyte is 5～7%.
6, the novel electrolyte that is used for lithium ion battery according to claim 1, the mass percent concentration that it is characterized in that highly reactive polymer monomeric additive in the novel electrolyte is 7～10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN02109812A CN1385918A (en) | 2002-05-22 | 2002-05-22 | Novel electrolyte for lithium ion cell |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN02109812A CN1385918A (en) | 2002-05-22 | 2002-05-22 | Novel electrolyte for lithium ion cell |
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| CN1385918A true CN1385918A (en) | 2002-12-18 |
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| CN02109812A Pending CN1385918A (en) | 2002-05-22 | 2002-05-22 | Novel electrolyte for lithium ion cell |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2866478A1 (en) * | 2004-02-12 | 2005-08-19 | Commissariat Energie Atomique | Lithium battery with protection against inappropriate utilization, notably to provide an energy source for portable equipment |
| WO2007045162A1 (en) | 2005-10-18 | 2007-04-26 | Byd Company Limited | An additive mixture of the electrolyte of lithium ion secondary batteries and the electrolyte of lithium ion secondary batteries including the said additive mixture |
| CN101577348B (en) * | 2009-05-15 | 2011-03-23 | 中南大学 | Multiplex overcharging protection functional electrolyte for lithium ion battery |
| CN101371397B (en) * | 2006-01-23 | 2011-12-07 | 株式会社Lg化学 | Non-aqueous-electrolyte and lithium secondary battery using the same |
| WO2014144056A1 (en) | 2013-03-15 | 2014-09-18 | Wildcat Discovery Technologies, Inc. | Electrolyte solutions for high energy cathode materials and methods for use |
| CN101673852B (en) * | 2008-09-11 | 2015-01-14 | 比亚迪股份有限公司 | Electrolyte additive and electrolyte and lithium ion battery containing same |
| US9236634B2 (en) | 2013-03-15 | 2016-01-12 | Wildcat Discorvery Technologies, Inc. | Electrolyte solutions for high cathode materials and methods for use |
| US9287586B1 (en) | 2015-01-16 | 2016-03-15 | Wildcat Discovery Technologies, Inc. | Electrolyte solutions for high energy cathode materials and methods for use |
| US9425485B1 (en) | 2015-03-27 | 2016-08-23 | Wildcat Discovery Technologies, Inc. | Electrolyte formulations for gas suppression and methods of use |
| US9912011B1 (en) | 2017-02-24 | 2018-03-06 | Wildcat Discovery Technologies, Inc | Electrolyte additives |
| US9985316B1 (en) | 2017-02-24 | 2018-05-29 | Wildcat Discovery Technologies, Inc | Electrolyte additives |
| CN114899478A (en) * | 2022-05-18 | 2022-08-12 | 湖南大学 | Carbazole nonaqueous electrolyte, preparation method thereof and lithium ion battery |
-
2002
- 2002-05-22 CN CN02109812A patent/CN1385918A/en active Pending
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005083819A3 (en) * | 2004-02-12 | 2006-06-01 | Commissariat Energie Atomique | Lithium battery which is protected in case of inappropriate use |
| CN102299379A (en) * | 2004-02-12 | 2011-12-28 | 原子能委员会 | Lithium battery with protection against inappropriate utilization |
| FR2866478A1 (en) * | 2004-02-12 | 2005-08-19 | Commissariat Energie Atomique | Lithium battery with protection against inappropriate utilization, notably to provide an energy source for portable equipment |
| WO2007045162A1 (en) | 2005-10-18 | 2007-04-26 | Byd Company Limited | An additive mixture of the electrolyte of lithium ion secondary batteries and the electrolyte of lithium ion secondary batteries including the said additive mixture |
| CN101371397B (en) * | 2006-01-23 | 2011-12-07 | 株式会社Lg化学 | Non-aqueous-electrolyte and lithium secondary battery using the same |
| CN101673852B (en) * | 2008-09-11 | 2015-01-14 | 比亚迪股份有限公司 | Electrolyte additive and electrolyte and lithium ion battery containing same |
| CN101577348B (en) * | 2009-05-15 | 2011-03-23 | 中南大学 | Multiplex overcharging protection functional electrolyte for lithium ion battery |
| CN105051965A (en) * | 2013-03-15 | 2015-11-11 | 野猫技术开发公司 | Electrolyte solutions for high energy cathode materials and methods for use |
| WO2014144056A1 (en) | 2013-03-15 | 2014-09-18 | Wildcat Discovery Technologies, Inc. | Electrolyte solutions for high energy cathode materials and methods for use |
| US9236634B2 (en) | 2013-03-15 | 2016-01-12 | Wildcat Discorvery Technologies, Inc. | Electrolyte solutions for high cathode materials and methods for use |
| US20160093918A1 (en) * | 2013-03-15 | 2016-03-31 | Wildcat Discovery Technologies, Inc. | Electrolyte Solutions for High Energy Cathode Materials and Methods for Use |
| EP2973834A4 (en) * | 2013-03-15 | 2016-10-19 | Wildcat discovery technologies inc | Electrolyte solutions for high energy cathode materials and methods for use |
| US11050084B2 (en) | 2013-03-15 | 2021-06-29 | Wildcat Discovery Technologies, Inc | Electrolyte solutions for high energy cathode materials and methods for use |
| US9287586B1 (en) | 2015-01-16 | 2016-03-15 | Wildcat Discovery Technologies, Inc. | Electrolyte solutions for high energy cathode materials and methods for use |
| US9425485B1 (en) | 2015-03-27 | 2016-08-23 | Wildcat Discovery Technologies, Inc. | Electrolyte formulations for gas suppression and methods of use |
| US9912011B1 (en) | 2017-02-24 | 2018-03-06 | Wildcat Discovery Technologies, Inc | Electrolyte additives |
| US9985316B1 (en) | 2017-02-24 | 2018-05-29 | Wildcat Discovery Technologies, Inc | Electrolyte additives |
| CN114899478A (en) * | 2022-05-18 | 2022-08-12 | 湖南大学 | Carbazole nonaqueous electrolyte, preparation method thereof and lithium ion battery |
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