CN103647110A - Ultralow temperature discharge electrolyte of novel lithium ion battery - Google Patents
Ultralow temperature discharge electrolyte of novel lithium ion battery Download PDFInfo
- Publication number
- CN103647110A CN103647110A CN201310645684.6A CN201310645684A CN103647110A CN 103647110 A CN103647110 A CN 103647110A CN 201310645684 A CN201310645684 A CN 201310645684A CN 103647110 A CN103647110 A CN 103647110A
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- electrolyte
- lithium
- lithium ion
- carbonate
- ion battery
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
- H01M2300/0008—Phosphoric acid-based
-
- 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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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to ultralow temperature discharge electrolyte of a novel lithium ion battery. The electrolyte comprises the following raw materials in percent by weight: component A, namely 10-15 percent of conductive lithium salt, component B, namely 80-90 percent of organic solvent and component C, namely 2-8 percent of additive. The electrolyte has extremely high electrochemical stability. The freezing point is lowered, the ion migration capability is improved, the electrical conductivity is improved, the lithium ion transfer resistance is reduced, and the wettability of the electrolyte on a diaphragm under low-temperature conditions and the penetrability of the lithium ion to the diaphragm are improved. Therefore, the electrolyte has the characteristics of being capable of normally working in an environment with temperature of 50 DEG C below zero and being stable in performance and excellent in cycle indicators.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of electrolysis of new type lithium ion battery of ultra-low temperature discharge
Background technology
Along with the lithium ion battery marketization deepens continuously, people are more and more higher to the expectation of battery performance.Commercial lithium-ion batteries has been difficult to meet the needs of key areas such as electric motor car, space technology and military affairs at present, it is not good that one of the main reasons is exactly battery performance under high and low temperature, and once widening working temperature agenda is the Important Problems that lithium ion battery is paid close attention to.
Because electrolyte is started with to improve temperature performance and has been proved to be feasible technological approaches, this is that the state of interface that the performance of electrolyte and both positive and negative polarity thereof form affects battery temperature performance to a great extent because as the ion conductor that plays the effect of passing in battery.In recent years, research institution has carried out more work around this problem both at home and abroad, has obtained many progress and experience, but has also needed field to carry out more deep research.
Summary of the invention
The object of the invention is by using fluoro class carbonate solvent to improve the ion transfer ability of lithium-ion electrolyte, improve conductivity, reduce the resistance that lithium ion transmits, improve electrolyte under cryogenic conditions to the wettability of barrier film and lithium ion the penetrability to barrier film.The lithium ion battery ultralow temperature cycle performance that adopts this electrolyte, capability retention all significantly improves.
Object of the present invention can reach by following measures:
An electrolyte for the new type lithium ion battery of ultra-low temperature discharge, is characterized in that: composed of the following components:
Component A: electric conducting lithium salt 10～15%;
B component: organic solvent 80～90%;
Component C additive 2%～8%;
This electrolyte 50 circulation volume conservation rates in the time of-50 ℃ are that 64.3%, 0.2C discharge capacity is 61.7%
Described electric conducting lithium salt is selected from: at least one in lithium hexafluoro phosphate, LiBF4, lithium perchlorate, hexafluoroarsenate lithium, dioxalic acid lithium borate, difluorine oxalic acid boracic acid lithium, two (trimethyl fluoride sulfonyl) imine lithium.
Described organic solvent is the mixture of propene carbonate, ethylene carbonate, methyl ethyl carbonate and Ethyl formate, and the mass ratio of described propene carbonate, ethylene carbonate, methyl ethyl carbonate and Ethyl formate is about 1: 4: 4: 4)
Described additive is fluoro carbonates solvent, this fluoro carbonates solvent bag is selected from a fluoro methyl carbonic acid vinyl acetate, difluorinated ethylene carbonate, three fluorinated ethylene carbonates, fluoropropylene carbonate, 4-tri-fluoro methyl carbonic acid vinyl acetate, two (trifluoromethyl) carbonic ester, two (2,2,2) one or more in-trifluoroethyl carbonic ester.
Beneficial effect:
Because fluoro carbonates solvent has strong electronegativity and low pole, electrolyte has very high electrochemical stability.Solidifying point reduces, and improves ion transfer ability, improves conductivity, reduces the resistance that lithium ion transmits, improve electrolyte under cryogenic conditions to the wettability of barrier film and lithium ion the penetrability to barrier film.Make electrolyte there is in the environment of-50 ℃ also normally the features such as work and smooth performance, cycle indicator be good.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.
Below by embodiment, the present invention is described further.
1, embodiment 1:
Mass percent is that the lithium hexafluoro phosphate of 2% fluoropropylene carbonate and 11% is dissolved in 87% organic solvent (propene carbonate, ethylene carbonate, methyl ethyl carbonate and Ethyl formate mass ratio are 1:4:4:4), after mixing, makes electrolyte.
2, embodiment 2:
Mass percent is that the lithium hexafluoro phosphate of a fluoro methyl carbonic acid vinyl acetate of 3% and 13% is dissolved in 84% organic solvent (propene carbonate, ethylene carbonate, methyl ethyl carbonate and Ethyl formate mass ratio are 1:4:4:4), after mixing, makes electrolyte.
3, embodiment 3:
Mass percent is that the lithium hexafluoro phosphate of 5% 4-tri-fluoro methyl carbonic acid vinyl acetate and 13.5% is dissolved in 81.5% organic solvent (propene carbonate, ethylene carbonate, methyl ethyl carbonate and Ethyl formate mass ratio are 1:4:4:4), after mixing, makes electrolyte.
4, embodiment 4:
Mass percent is that the lithium hexafluoro phosphate of 4% two (trifluoromethyl) carbonic esters and 13% is dissolved in 83% organic solvent (propene carbonate, ethylene carbonate, methyl ethyl carbonate and Ethyl formate mass ratio are 1:4:4:4), after mixing, makes electrolyte.
5, embodiment 5:
Mass percent is 3% 2 (2,2,2)-trifluoroethyl carbonic ester, 4% difluorinated ethylene carbonate and 11.5% lithium hexafluoro phosphate are dissolved in 81.5% organic solvent (propene carbonate, ethylene carbonate, methyl ethyl carbonate and Ethyl formate mass ratio are 1:4:4:4), after mixing, make electrolyte.
6, comparative example:
The lithium hexafluoro phosphate of mass percent 11.5% is dissolved in 88.5% organic solvent (propene carbonate, ethylene carbonate, methyl ethyl carbonate mass ratio for, Ethyl formate mass ratio be 1:4:4:4), after mixing, makes electrolyte.
Electrolyte described in embodiment and comparative example is injected after cobalt acid lithium battery, and-50 ℃ of high temperature experimental datas are as follows:
Visible, the lithium battery of being prepared by electrolyte described in the embodiment of the present invention 1～5 is compared the lithium battery of being prepared by comparative example, embodiment 1,2,3,4 electrolyte are compared comparative example electrolyte, and owing to using fluoro class carbonates solvent, its low-temperature circulating performance is relative with discharge capability to be improved.Embodiment 5 electrolyte are used 3% 2 (2,2,2)-trifluoroethyl carbonic ester and 4% difluorinated ethylene carbonate as additive, and battery is significantly improved at low-temperature circulating capability retention and-50 ℃ of 0.2C discharge capabilities of-50 ℃.
Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (4)
1. an electrolyte for the new type lithium ion battery of ultra-low temperature discharge, is characterized in that: composed of the following components:
Component A: electric conducting lithium salt 10～15%;
B component: organic solvent 80～90%;
Component C additive 2%～8%;
This electrolyte 50 circulation volume conservation rates in the time of-50 ℃ are that 64.3%, 0.2C discharge capacity is 61.7%.
2. the electrolyte of the new type lithium ion battery of a kind of ultra-low temperature discharge as claimed in claim 1, is characterized in that described electric conducting lithium salt is selected from: at least one in lithium hexafluoro phosphate, LiBF4, lithium perchlorate, hexafluoroarsenate lithium, dioxalic acid lithium borate, difluorine oxalic acid boracic acid lithium, two (trimethyl fluoride sulfonyl) imine lithium.
3. the electrolyte of the new type lithium ion battery of a kind of ultra-low temperature discharge as claimed in claim 1, it is characterized in that described organic solvent is the mixture of propene carbonate, ethylene carbonate, methyl ethyl carbonate and Ethyl formate, the mass ratio of described propene carbonate, ethylene carbonate, methyl ethyl carbonate and Ethyl formate is about 1:4:4:4.
4. the electrolyte of the new type lithium ion battery of a kind of ultra-low temperature discharge as claimed in claim 1, it is characterized in that described additive is fluoro carbonates solvent, this fluoro carbonates solvent bag is selected from a fluoro methyl carbonic acid vinyl acetate, difluorinated ethylene carbonate, three fluorinated ethylene carbonates, fluoropropylene carbonate, 4-tri-fluoro methyl carbonic acid vinyl acetate, two (trifluoromethyl) carbonic ester, two (2,2,2) one or more of-trifluoroethyl carbonic ester.
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| CN201310645684.6A CN103647110A (en) | 2013-12-06 | 2013-12-06 | Ultralow temperature discharge electrolyte of novel lithium ion battery |
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| CN201310645684.6A CN103647110A (en) | 2013-12-06 | 2013-12-06 | Ultralow temperature discharge electrolyte of novel lithium ion battery |
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| CN103647110A true CN103647110A (en) | 2014-03-19 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105406123A (en) * | 2015-12-25 | 2016-03-16 | 苏州格瑞动力电源科技有限公司 | Lithium ion battery electrolyte |
| CN105449282A (en) * | 2014-08-27 | 2016-03-30 | 江苏华盛精化工股份有限公司 | A fluoro-propylene carbonate based electrolyte and a lithium ion battery |
| CN106099185A (en) * | 2016-07-05 | 2016-11-09 | 惠州市豪鹏科技有限公司 | A kind of electrolyte and include the lithium ion battery of this electrolyte |
| CN107171023A (en) * | 2017-05-17 | 2017-09-15 | 中国第汽车股份有限公司 | A kind of low temperature electrolytes for Li-ion batteries |
| CN108123173A (en) * | 2017-12-14 | 2018-06-05 | 成都新柯力化工科技有限公司 | A kind of electrolyte of low-temperature lithium ion battery and lithium ion battery |
| CN109659610A (en) * | 2018-12-14 | 2019-04-19 | 河南华瑞高新材料有限公司 | A kind of function electrolyte of the lithium ion battery of ultra-low temperature discharge |
| CN109687022A (en) * | 2018-12-25 | 2019-04-26 | 杉杉新材料（衢州）有限公司 | The electrolyte of a kind of fluoride solvent and pyridined additives and lithium ion battery using the electrolyte |
| CN110998954A (en) * | 2017-11-28 | 2020-04-10 | 株式会社Lg化学 | Polymer electrolyte for secondary battery and secondary battery including the same |
| CN112366353A (en) * | 2020-11-09 | 2021-02-12 | 徐文忠 | Lithium ion battery electrolyte containing propylene carbonate |
| CN115692837A (en) * | 2022-11-15 | 2023-02-03 | 楚能新能源股份有限公司 | Low-temperature electrolyte for cylindrical battery, preparation method and lithium battery |
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| CN101383433A (en) * | 2008-10-17 | 2009-03-11 | 汕头市金光高科有限公司 | Stabilizer for non-water electrolysis and non-water electrolysis containing the stabilizer |
| CN101826635A (en) * | 2010-04-09 | 2010-09-08 | 广州天赐高新材料股份有限公司 | Polymer electrolyte for lithium battery and manufacturing method of battery thereof |
| CN102082295A (en) * | 2010-12-29 | 2011-06-01 | 东莞市杉杉电池材料有限公司 | Electrolyte of lithium-ion secondary battery |
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Patent Citations (3)
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| CN101383433A (en) * | 2008-10-17 | 2009-03-11 | 汕头市金光高科有限公司 | Stabilizer for non-water electrolysis and non-water electrolysis containing the stabilizer |
| CN101826635A (en) * | 2010-04-09 | 2010-09-08 | 广州天赐高新材料股份有限公司 | Polymer electrolyte for lithium battery and manufacturing method of battery thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105449282A (en) * | 2014-08-27 | 2016-03-30 | 江苏华盛精化工股份有限公司 | A fluoro-propylene carbonate based electrolyte and a lithium ion battery |
| CN105449282B (en) * | 2014-08-27 | 2018-08-07 | 江苏长园华盛新能源材料有限公司 | Fluoropropylene carbonate base electrolyte and lithium ion battery |
| CN105406123A (en) * | 2015-12-25 | 2016-03-16 | 苏州格瑞动力电源科技有限公司 | Lithium ion battery electrolyte |
| CN106099185A (en) * | 2016-07-05 | 2016-11-09 | 惠州市豪鹏科技有限公司 | A kind of electrolyte and include the lithium ion battery of this electrolyte |
| CN107171023A (en) * | 2017-05-17 | 2017-09-15 | 中国第汽车股份有限公司 | A kind of low temperature electrolytes for Li-ion batteries |
| CN110998954A (en) * | 2017-11-28 | 2020-04-10 | 株式会社Lg化学 | Polymer electrolyte for secondary battery and secondary battery including the same |
| US11670800B2 (en) | 2017-11-28 | 2023-06-06 | Lg Energy Solution, Ltd. | Polymer electrolyte for secondary battery and secondary battery including the same |
| CN108123173A (en) * | 2017-12-14 | 2018-06-05 | 成都新柯力化工科技有限公司 | A kind of electrolyte of low-temperature lithium ion battery and lithium ion battery |
| CN109659610A (en) * | 2018-12-14 | 2019-04-19 | 河南华瑞高新材料有限公司 | A kind of function electrolyte of the lithium ion battery of ultra-low temperature discharge |
| CN109687022A (en) * | 2018-12-25 | 2019-04-26 | 杉杉新材料（衢州）有限公司 | The electrolyte of a kind of fluoride solvent and pyridined additives and lithium ion battery using the electrolyte |
| CN112366353A (en) * | 2020-11-09 | 2021-02-12 | 徐文忠 | Lithium ion battery electrolyte containing propylene carbonate |
| CN112366353B (en) * | 2020-11-09 | 2021-11-02 | 徐文忠 | Lithium ion battery electrolyte containing propylene carbonate |
| CN115692837A (en) * | 2022-11-15 | 2023-02-03 | 楚能新能源股份有限公司 | Low-temperature electrolyte for cylindrical battery, preparation method and lithium battery |
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Application publication date: 20140319 |