CN103456982A - Functional electrolyte for improving charge-discharge efficiency of lithium ion battery and application thereof - Google Patents
Functional electrolyte for improving charge-discharge efficiency of lithium ion battery and application thereof Download PDFInfo
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- CN103456982A CN103456982A CN2013104286893A CN201310428689A CN103456982A CN 103456982 A CN103456982 A CN 103456982A CN 2013104286893 A CN2013104286893 A CN 2013104286893A CN 201310428689 A CN201310428689 A CN 201310428689A CN 103456982 A CN103456982 A CN 103456982A
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- ion battery
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- 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
Abstract
The invention discloses functional electrolyte for improving the charge-discharge efficiency of a lithium ion battery. The functional electrolyte is characterized by consisting of the following components in percentage by weight: 80%-90% of an organic solvent, 0.1%-2% of functional additive, and the balance being lithium salts, wherein the lithium salts are one or more of LiPF6, LiBF4, and LiTFSI, the organic solvent is a cyclic ester compound or a chain ester compound, and the structure general expression of the functional additive is R-C6H3-(OCH3)2, wherein R is H, halogen, or -NO2, and two -OCH3 are located in ortho-position or para-position on a benzene ring. The functional electrolyte provided by the invention is applicable to the lithium ion battery made from lithium manganate, a ternary material, nickel lithium manganate and lithium titanate, and is capable of improving the charge-discharge efficiency of the lithium ion battery and further effectively increasing the capacity and prolonging the cycle life of the lithium ion battery.
Description
Technical field
The invention belongs to technical field of lithium ion, relate to a kind of raising and using function electrolyte and the application thereof as anodal lithium ion battery efficiency for charge-discharge of LiMn2O4, ternary material and nickel manganese material.
Background technology
Lithium ion battery, because it has that energy density is large, operating voltage is high, the characteristics of lightweight and non-environmental-pollution, is widely used in the portable type electronic product equipment such as mobile phone, notebook computer.Therefore, its combination property is had relatively high expectations.In the charge and discharge process of lithium ion battery, the irreversible reduction of lithium ion, can reduce the efficiency for charge-discharge of battery, thereby affect the useful life of battery.In addition, in charging process, the active site place local voltage of electrode surface is too high, can cause electrolyte decomposition, thereby has a strong impact on cycle life and the fail safe of battery, even causes the complete failure of battery.
The interface performance of lithium ion cell electrode and electrolyte is poor is the one of the main reasons that causes capacity attenuation in cyclic process.There is certain defect in electrolyte commonly used at present.Especially in battery charge and discharge process, the interfacial activity point place that electrode active material contacts with electrolyte, have a small amount of electrolyte and decompose.The decomposition reaction meeting of electrolyte consumes a certain amount of lithium ion, affects the efficiency for charge-discharge of battery.Thereby serious capacity attenuation, in long-term cyclic process, occurs in battery, therefore can not meet its use in lithium ion battery.These problems are mainly by due to anodal and interface performance that electrolyte is poor.Therefore, develop effective functional electrolysis liquid, the character of improving active anode compartment and electrolyte contact interface is necessary.
Summary of the invention
Main purpose of the present invention is for the low problem of current lithium ion battery efficiency for charge-discharge, proposes to improve the function electrolyte of lithium ion battery efficiency for charge-discharge, for improving interface performance anodal and electrolyte, thereby improves the efficiency for charge-discharge of battery.
Another object of the present invention is to provide a kind of application of above-mentioned functions electrolyte aspect lithium ion battery that contain, in order to improve the compatibility of anodal and electrolyte, improve capacity of lithium ion battery and capability retention;
For achieving the above object, the present invention has adopted following technical scheme:
A kind of function electrolyte that improves the lithium ion battery efficiency for charge-discharge, is characterized in that,
Described function electrolyte is comprised of following component by mass percentage: organic solvent 80%-90% and functional additive 0.1%-2%, and surplus is lithium salts, take the function electrolyte gross mass as 100%;
Wherein, described lithium salts is LiPF
6, LiBF
4with one or more in LiTFSI, described organic solvent is cyclic ester compound or chain ester compounds, and the general structure of described functional additive is R-C
6h
3-(OCH
3)
2, wherein, R be H, halogen or-NO
2, two-OCH
3be positioned at ortho position or contraposition on phenyl ring.
Function electrolyte according to above-mentioned raising lithium ion battery efficiency for charge-discharge of the present invention, is characterized in that, described functional additive is 1,2-dimethoxy-4 '-nitrobenzene, 1,4-dimethoxy-2-nitrobenzene, 1,2-dimethoxy-4 '-fluorobenzene, Isosorbide-5-Nitrae-dimethoxy-2-fluorobenzene, 1,4-dimethoxy-2-bromobenzene, 1,2-dimethoxy-4 ' bromobenzene, Isosorbide-5-Nitrae-dimethoxy-2 chlorobenzene, 1,2-dimethoxy-4 '-chlorobenzene, 1, wherein one or more of 2-dimethoxy benzene and Isosorbide-5-Nitrae-dimethoxy benzene; Described organic solvent is selected from two or more the organic solvent in ethylene carbonate, propene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate and fluorinated ethylene carbonate; Described lithium salts is LiPF
6, LiTFSI and LiBF
4in one or more, and lithium salts as electrolyte, the concentration in electrolyte is 0.8-1.5mol/L.
The present invention also provides the application in lithium ion battery according to above-mentioned functions electrolyte, and advantageous applications is anodal lithium ion battery at spinel lithium manganate, ternary material, nickel LiMn2O4 and lithium titanate material.
In the general formula of component function additive of the present invention, oxidative decomposition, under certain potentials, can occur in the molecule that on phenyl ring, two methoxyl groups are contained at contraposition or ortho position, on anodal surface, forms stable solid electrolyte interface film (SEI film).This additive application is in lithium ion battery, and preferentially electrolyte decomposes, and product is attached to the positive electrode surface, can avoid electrolyte directly to contact with material, prevents at pole piece active site place electrolyte generation decomposition reaction.Thereby improve the character of active anode compartment and electrolyte contact interface.
Function electrolyte of the present invention beneficial effect compared with prior art is: function electrolyte of the present invention by adding functional additive in lithium-ion battery electrolytes, form the stable interfacial film of one deck at electrode surface, interfacial film has suppressed electrolyte solvent and has decomposed at the catalytic oxidation of electrode surface, effectively raise efficiency for charge-discharge and the capability retention of battery, improved the compatibility of active anode compartment material and electrolyte.
The accompanying drawing explanation
Fig. 1 adopts the present invention to improve the embodiment 1-3 of function electrolyte of lithium ion battery efficiency for charge-discharge and the efficiency for charge-discharge figure of comparative example 1.
Fig. 2 (a) is the lithium ion battery capacity circulating curve at room temperature that adopts the electrolyte of the function electrolyte of the embodiment of the present invention 2 and comparative example 1; 2 (b) are the capacity circulating curve of lithium ion battery under 55 ℃ of the electrolyte of the function electrolyte of the embodiment of the present invention 1 and comparative example 1.
Fig. 3 is that the embodiment of the present invention 2 and comparative example 1 are applied to lithium ion battery, changes into the AC impedance figure of rear battery.
Embodiment
The function electrolyte and the applicable cases thereof that the present invention are improved to the lithium ion battery efficiency for charge-discharge below in conjunction with drawings and Examples are further described.
Prepare function electrolyte
Being formulated in the glove box that is full of high-purity argon gas of function electrolyte carried out, H
2o≤1ppm, temperature is at 25 ℃.The electrolyte lithium salts is selected LiPF
6solvent contains ethylene carbonate (EC), diethyl carbonate (DEC), and vinylene carbonate (VC) additive, improve the functional additive of efficiency for charge-discharge and select 1,4-dimethoxy-2-fluorobenzene (embodiment 1), 1,2-dimethoxy-4 '-nitrobenzene (embodiment 2), Isosorbide-5-Nitrae-dimethoxy benzene (embodiment 3), structural formula are as follows:
The electrolyte prescription of specific embodiment and comparative example 1 is as shown in table 1.
The electrolyte prescription of table 1 embodiment 1-3 and comparative example 1
In table: the mass percent of VC and additive (Isosorbide-5-Nitrae-dimethoxy-2-fluorobenzene, 1,2-dimethoxy-4 '-nitrobenzene or Isosorbide-5-Nitrae-dimethoxy benzene) is to take the function electrolyte gross mass as 100%.
The application performance test
With LiNi
0.5mn
1.5o
4for positive pole, take the lithium sheet as negative pole, be assembled into the CR2032 button cell, prepared electrolyte is estimated.Battery adopts the 0.2C electric current to be changed into, and adopts the 1C electric current to carry out the cycle performance test, and the charging/discharging voltage interval is 3.5-4.95V.
To the battery changed into, adopt the PAR2273 electrochemical workstation to carry out ac impedance measurement, the EIS frequency range is 100kHz-10mHz, and disturbing signal is 5mV.
The efficiency for charge-discharge numerical value of embodiment 1-3 and comparative example 1 as shown in Figure 1, provides the efficiency for charge-discharge numerical value of circulation first and the 100th circulation in table 2.
The efficiency for charge-discharge of table 2 battery
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| First | 99.6% | 99.7% | 99.6% | 99.6% |
| The 100th time | 99.2% | 99.4% | 99.1% | 97.8% |
After 100 circulations of embodiment 2 and comparative example 1 battery, capability retention is as shown in table 3.The capacity circulating of embodiment 2 and comparative example 1 as shown in Figure 2.
Capability retention after 100 circulations of table 3 battery
| ? | Embodiment 2 | Comparative example 1 |
| Conservation rate (25 ℃) | 99.1% | 95.3% |
| Conservation rate (55 ℃) | 99.4% | 96.4% |
Fig. 3 can find out, the battery of embodiment 2, and there are two semicircles in impedance diagram, has less interfacial film impedance.Only there is a semicircle in comparative example 1 impedance, and impedance is greater than the battery impedance value of embodiment 2.After illustrating that this functional additive adds, LiNi
0.5mn
1.5o
4electrode surface forms fine and close one deck SEI film, and this tunic can avoid electrolyte directly to contact with electrode surface, and guard electrode, prevent electrolyte decomposition, thereby improves the efficiency for charge-discharge of battery.
By the electrolyte property of comparing embodiment and comparative example, can find out, this functional additive can effectively improve the efficiency for charge-discharge of lithium ion battery.And, formed the SEI film of stable densification at electrode surface, reduced the electrode interface membrane impedance, increased the capacity of battery and the capability retention after circulation.
Claims (5)
1. a function electrolyte that improves the lithium ion battery efficiency for charge-discharge, is characterized in that,
Described function electrolyte is comprised of following component by mass percentage: organic solvent 80%-90% and functional additive 0.1%-2%, and surplus is lithium salts, take the function electrolyte gross mass as 100%;
Wherein, described lithium salts is LiPF
6, LiBF
4with one or more in LiTFSI, described organic solvent is cyclic ester compound or chain ester compounds, and the general structure of described functional additive is R-C
6h
3-(OCH
3)
2, wherein, R be H, halogen or-NO
2, two-OCH
3be positioned at ortho position or contraposition on phenyl ring.
2. a kind of function electrolyte that improves the lithium ion battery efficiency for charge-discharge according to claim 1, it is characterized in that, described functional additive is 1,2-dimethoxy-4 '-nitrobenzene, 1,4-dimethoxy-2-nitrobenzene, 4-fluoro-1,2-dimethoxy benzene, 2-fluoro-1,4-dimethoxy benzene, 2-bromo-1,4-dimethoxy benzene, 4-bromo-1,2-dimethoxy benzene, the chloro-Isosorbide-5-Nitrae-dimethoxy benzene of 2-, 4-are chloro-1,2-dimethoxy benzene, 1, wherein one or more of 2-dimethoxy benzene and Isosorbide-5-Nitrae-dimethoxy benzene.
3. a kind of function electrolyte that improves the lithium ion battery efficiency for charge-discharge according to claim 1, it is characterized in that, described organic solvent is selected from two or more the organic solvent in ethylene carbonate, propene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate and fluorinated ethylene carbonate.
4. the application of function electrolyte as described as claim 1～3 any one in lithium ion battery.
5. application according to claim 4, is characterized in that, described lithium ion battery is that spinel lithium manganate, ternary material, nickel LiMn2O4 and lithium titanate material are anodal lithium ion battery.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105161757A (en) * | 2015-07-24 | 2015-12-16 | 张家港市国泰华荣化工新材料有限公司 | Lithium-ion battery electrolyte containing redox overcharge protecting additive |
| CN117239231A (en) * | 2022-10-12 | 2023-12-15 | 哈尔滨工业大学 | Electrolyte additive for lithium battery, electrolyte and preparation method of electrolyte |
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| US20030157413A1 (en) * | 2002-02-15 | 2003-08-21 | Chen Chun-Hua | Lithium ion battery with improved safety |
| CN101000970A (en) * | 2006-01-11 | 2007-07-18 | 比亚迪股份有限公司 | Electrolyte and lithium ion battery containing the electrolyte and preparation method thereof |
| CN101510622A (en) * | 2008-02-14 | 2009-08-19 | 比亚迪股份有限公司 | Electrolyte for lithium ion secondary battery and battery containing the electrolyte |
| CN101577348A (en) * | 2009-05-15 | 2009-11-11 | 中南大学 | Multiplex overcharging protection functional electrolyte for lithium ion battery |
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2013
- 2013-09-18 CN CN2013104286893A patent/CN103456982A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030077515A1 (en) * | 2001-04-02 | 2003-04-24 | Chen George Zheng | Conducting polymer-carbon nanotube composite materials and their uses |
| US20030157413A1 (en) * | 2002-02-15 | 2003-08-21 | Chen Chun-Hua | Lithium ion battery with improved safety |
| CN101000970A (en) * | 2006-01-11 | 2007-07-18 | 比亚迪股份有限公司 | Electrolyte and lithium ion battery containing the electrolyte and preparation method thereof |
| CN101510622A (en) * | 2008-02-14 | 2009-08-19 | 比亚迪股份有限公司 | Electrolyte for lithium ion secondary battery and battery containing the electrolyte |
| CN101577348A (en) * | 2009-05-15 | 2009-11-11 | 中南大学 | Multiplex overcharging protection functional electrolyte for lithium ion battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105161757A (en) * | 2015-07-24 | 2015-12-16 | 张家港市国泰华荣化工新材料有限公司 | Lithium-ion battery electrolyte containing redox overcharge protecting additive |
| CN117239231A (en) * | 2022-10-12 | 2023-12-15 | 哈尔滨工业大学 | Electrolyte additive for lithium battery, electrolyte and preparation method of electrolyte |
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Application publication date: 20131218 |