CN105680097A - High-safety lithium-ion battery electrolyte solution - Google Patents
High-safety lithium-ion battery electrolyte solution Download PDFInfo
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- CN105680097A CN105680097A CN201610047321.6A CN201610047321A CN105680097A CN 105680097 A CN105680097 A CN 105680097A CN 201610047321 A CN201610047321 A CN 201610047321A CN 105680097 A CN105680097 A CN 105680097A
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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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
The invention discloses a high-safety lithium-ion battery electrolyte solution, and belongs to the field of lithium-ion batteries. Main components of the electrolyte solution disclosed by the invention comprise an organic solvent, an electrolyte and additives, wherein at least a high flash point solvent is contained in the organic solvent, and the additives comprise a film additive and a flame retardant additive. The molar concentration of the electrolyte in the organic solvent is 0.8-1.5 mol/L, and the weight percentages of the additives in the electrolyte solution are 2-8% and 1-2% respectively. According to the high-safety lithium-ion battery electrolyte solution disclosed by the invention, by using the method that the high flash point solvent is combined with a small amount of the flame retardant additive for use, the electrolyte solution has a good flame retardant effect, is difficult to ignite, and is relatively short in self-extinguished time. When the electrolyte solution is used on the lithium-ion batteries, the safety performance of the batteries can be improved.
Description
Technical field
The present invention relates to field of lithium ion battery, particularly to a kind of high security lithium ion battery electrolyte.
Background technology
In recent years, along with the development of science and technology, people are more urgent to the demand of lithium ion battery with high energy density, and the running voltage improving lithium ion battery at present is considered as improve the effective way of its energy density. But, conventional conventional carbonate class electrolyte under high voltages easily with the generation side reaction of positive electrode surface, when these chemical reaction liberated heats can not be evacuated in time, a series of chemical reaction and will be caused, battery temperature sharply raises, ultimately result in the burning of battery, blast time serious. On the other hand, lithium rechargeable battery releases a large amount of heat at excessive discharge and recharge, short circuit and big electric current when working long hours, these heats become the potential safety hazard of inflammable electrolyte, it is possible to cause calamitous thermal breakdown even battery explosion. Therefore, safety issue has become as the important prerequisite of lithium ion battery market innovation, particularly proposes requirement higher, that update in the safety to battery of applying in the fields such as electric automobile.
In order to improve lithium ion battery security; researcher makes a lot of effort from aspects such as outside batteries management, inside battery material and electrolyte, as adopted positive temperature coefficient thermo-sensitive material (PTC) protection board, material modification, solid electrolyte, flame-retardant electrolyte etc. Research and develop non-flammable electrolyte system, be the effective way solving lithium ion battery safety problem.
The lithium-ion electrolyte that US Patent No. 6589697 is announced have employed the phosphoric acid esters such as trimethyl phosphate (TMP) as electrolysis additive, reduces the combustibility of electrolyte. But these additives mostly have high viscosity, high freezing point, and when using as flame-retardant additive, add more than 10% and just there is flame retardant effect, and flame-retardant additive adds the too much bigger negative effect that can the performance of battery be produced, therefore, it is badly in need of exploitation and can not affect the electrolyte realizing fire resistance on the basis of lithium ion battery key property.
When there is the main solvent that solvent is electrolyte of high boiling point and high-flash, the flash-point of electrolyte can be correspondingly improved, electrolyte is made to be difficult to light, A.Abouimrane etc. report the Li4Ti5O12/LiMn2O4 battery prepared with sulfone kind solvent for electrolyte, cycle performance is good and difficult point combustion (.ElectrochemCommun, 2009,11 (5): 1073-1076.). Patent US0204857 reports with LiBF4 for lithium salts, 10% ~ 30% high-flash, high boiling γ-BL+70% ~ 90% the flame-retardant electrolyte that EC is solvent. High boiling point, high flash solvent addition improve the flash-point of electrolyte, make electrolyte difficult point fire, but the self-extinguishing time of electrolyte can not be made to reduce.
Summary of the invention
It is an object of the invention to provide a kind of high security lithium ion battery electrolyte, make electrolyte have be difficult to light, self-extinguishing time short, meanwhile, the performance that battery performance impact is less.
The technical scheme is that a kind of high security lithium ion battery electrolyte, it is characterized in that: electrolyte main component includes organic solvent, electrolyte and additive, including at least there being a kind of high flash solvent in described organic solvent, described additive includes film additive and flame-retardant additive; Electrolyte quota method is; in the glove box of argon shield; high-purity organic solvent is added mix homogeneously by proportioning; it is then slowly added into electrolyte lithium salt; it is uniformly mixed, finally additive is separately added in above-mentioned mixed solution, is uniformly mixed; stand a period of time, the high security lithium ion battery electrolyte of the present invention can be obtained.
Electrolyte molar concentration in organic solvent is 0.8 ~ 1.5mol/L.
Preferred electrolyte molar concentration in organic solvent is 1 ~ 1.2mol/L.
High flash solvent of the present invention is one or more in following several solvent: fluorinated solvents, sulfone kind solvent, cyclic carboxylic esters.
Described fluorinated solvents be preferably fluorinated ethylene carbonate (FEC), 1,1,2,2-tetra-fluoro ethyl-2,2,3,3-tetrafluoro propyl ethers etc., sulfone kind solvent is preferably sulfolane (TMS), dimethyl sulfite (DMS) etc., and cyclic carboxylic esters is preferably gamma-butyrolacton (BL).
In additive of the present invention, film for additive is: the one in vinylene carbonate, vinylethylene carbonate, fluorinated ethylene carbonate.
Described flame-retardant additive is the one in trimethyl phosphate, triphenyl phosphate, hexamethyl phosphine nitrile etc.
Film for additive percetage by weight in the electrolytic solution is 1 ~ 2%, flame-retardant additive percetage by weight in the electrolytic solution is 5 ~ 8%.
Wherein, moisture < 10ppm, oxygen < 10ppm in the glove box of argon shield.
The electrolyte combustibility test of the present invention can take following method: ceramic fiber paper thick for 5mm is cut into the strip of 15 × 20mm size be placed in thermostatic drying chamber 85 DEG C dry 8 hours. Copper wire is cut into 10cm length, is hooked in top about 5mm place, ceramic fiber paper center, weigh the gross mass m1 of ceramic fiber paper and copper wire, be accurate to 0.01g. Ceramic fiber paper is put in 100ml beaker, pour electrolyte into and soak 5 minutes, take out ceramic fiber paper, weigh the gross mass m2 after soaking electrolyte with weight reduction, be accurate to 0.01g. The ceramic fiber paper soaking electrolyte is hung on iron stand, lights, record after burning things which may cause a fire disaster leaves to the time that ceramic fiber paper extinguishes, calculate self-extinguishing time:。
The invention have the benefit that and be simultaneously introduced in lithium-ion battery electrolytes by high flash solvent and a small amount of flame-retardant additive, electrolyte can not only be made to be difficult to light, and meanwhile, the electrolyte after lighting is owing to containing a small amount of flame-retardant additive, self-extinguishing time is shorter. Thus battery performance impact is less.
Detailed description of the invention
The present invention will be further elaborated by the examples below; But the present invention does not do any pro forma restriction, and any purport not necessarily departing from the present invention, and the change that the present invention is done more or change, all within protection scope of the present invention.
Embodiment 1
A kind of high security lithium ion battery electrolyte, at full argon (H2O < 10ppm, O2< 10ppm) glove mutually in, by organic solvent ethylene carbonate (EC) that weight ratio is 1:4,1,1,2,2-tetra-fluoro ethyl-2,2,3,3-tetrafluoro propyl ether mix homogeneously; Add electric conducting lithium salt LiPF afterwards6So that it is concentration in organic solvent is 1.0mol/L, is finally separately added into trimethyl phosphate (TMP), and consumption is 5wt.%; Vinylene carbonate (VC), consumption is 2wt%, mix homogeneously, stands, namely obtains described high security lithium ion battery electrolyte.
Embodiment 2
A kind of high security lithium ion battery electrolyte, at full argon (H2O < 10ppm, O2< 10ppm) glove mutually in, by organic solvent ethylene carbonate (EC), fluorinated ethylene carbonate (FEC) mix homogeneously; The weight ratio of EC and FEC is EC:FEC=1:1, adds electric conducting lithium salt LiPF afterwards6So that it is concentration in organic solvent is 1.2mol/L, is finally separately added into trimethyl phosphate (TPP), and consumption is 5wt.%; Vinylene carbonate (VC), consumption is 1wt%, mix homogeneously, stands, namely obtains described high security lithium ion battery electrolyte.
Embodiment 3
A kind of high security lithium ion battery electrolyte, at full argon (H2O < 10ppm, O2< 10ppm) glove mutually in, by organic solvent ethylene carbonate (EC), dimethyl sulfite (DMS) mix homogeneously; The weight ratio of EC and DMS is EC:DMS=3:7, adds electric conducting lithium salt LiPF afterwards6So that it is concentration in organic solvent is 1.5mol/L, is finally separately added into trimethyl phosphate (TMP), and consumption is 5wt.%; Vinylene carbonate (VC), consumption is 1wt%, mix homogeneously, stands, namely obtains described high security lithium ion battery electrolyte.
Embodiment 4
A kind of high security lithium ion battery electrolyte, at full argon (H2O < 10ppm, O2< 10ppm) glove mutually in, by organic solvent ethylene carbonate (EC), sulfolane (TMS), Ethyl methyl carbonate (EMC) mix homogeneously; Weight ratio is EC:TMS:GBL=3:2:5, adds electric conducting lithium salt LiPF afterwards6So that it is concentration in organic solvent is 1mol/L, is finally separately added into triphenyl phosphate (TPP), and consumption is 5wt.%; Vinylene carbonate (VC), consumption is 1.5wt%, mix homogeneously, stands, namely obtains described high security lithium ion battery electrolyte.
Embodiment 5
A kind of high security lithium ion battery electrolyte, at full argon (H2O < 10ppm, O2< 10ppm) glove mutually in, by organic solvent ethylene carbonate (EC), Allyl carbonate (PC), gamma-butyrolacton (BL) mix homogeneously; Weight ratio is EC:PC:BL=2:1:7, adds electric conducting lithium salt LiPF afterwards6So that it is concentration in organic solvent is 1mol/L, is finally separately added into trimethyl phosphate (TMP), and consumption is 5wt.%; Vinylene carbonate (VC), consumption is 1wt%, mix homogeneously, stands, namely obtains described high security lithium ion battery electrolyte.
Embodiment 6
A kind of high security lithium ion battery electrolyte, at full argon (H2O < 10ppm, O2< 10ppm) glove mutually in, by organic solvent ethylene carbonate (EC), Allyl carbonate (PC), gamma-butyrolacton (BL) mix homogeneously; Weight ratio is EC:PC:BL=2:1:7, adds electric conducting lithium salt LiPF afterwards6So that it is concentration in organic solvent is 0.8mol/L, is finally separately added into trimethyl phosphate (TMP), and consumption is 8wt.%; Vinylene carbonate (VC), consumption is 1wt%, mix homogeneously, stands, namely obtains described high security lithium ion battery electrolyte.
Embodiment 7
A kind of high security lithium ion battery electrolyte, at full argon (H2O < 10ppm, O2< 10ppm) glove mutually in, by organic solvent ethylene carbonate (EC), Allyl carbonate (PC), gamma-butyrolacton (BL) mix homogeneously; Weight ratio is EC:PC:BL=2:1:7, adds electric conducting lithium salt LiPF afterwards6So that it is concentration in organic solvent is 1mol/L, is finally separately added into trimethyl phosphate (TMP), and consumption is 2wt.%; Vinylene carbonate (VC), consumption is 1wt%, mix homogeneously, stands, namely obtains described high security lithium ion battery electrolyte.
Embodiment 8
A kind of high security lithium ion battery electrolyte, at full argon (H2O < 10ppm, O2< 10ppm) glove mutually in, by organic solvent ethylene carbonate (EC), dimethyl sulfite (DMS) mix homogeneously; The weight ratio of EC and DMS is EC:DMS=3:7, adds electric conducting lithium salt LiPF afterwards6So that it is concentration in organic solvent is 1mol/L, is finally separately added into hexamethyl phosphine nitrile (HMPN), and consumption is 5wt.%; PS (1,3-PS), consumption is 1.5%, mix homogeneously, stands, namely obtains described high security lithium ion battery electrolyte.
Embodiment 9
A kind of high security lithium ion battery electrolyte, at full argon (H2O < 10ppm, O2< 10ppm) glove mutually in, by organic solvent ethylene carbonate (EC), gamma-butyrolacton (BL) mix homogeneously; The weight ratio of EC and BL is EC:BL=1:1, adds electric conducting lithium salt LiPF afterwards6So that it is concentration in organic solvent is 1mol/L, is finally separately added into trimethyl phosphate (TMP), and consumption is 5wt.%; Vinylene carbonate (VC), consumption is 1wt%, mix homogeneously, stands, namely obtains described high security lithium ion battery electrolyte.
Comparative example 1
At full argon (H2O < 10ppm, O2< 10ppm) glove mutually in, by organic solvent ethylene carbonate (EC), dimethyl carbonate (DMC) mix homogeneously; The weight ratio of EC and DMC is EC:DMC=3:7, adds electric conducting lithium salt LiPF afterwards6So that it is concentration in organic solvent is 1mol/L, mix homogeneously.
Comparative example 2
At full argon (H2O < 10ppm, O2< 10ppm) glove mutually in, by organic solvent ethylene carbonate (EC), gamma-butyrolacton (BL) mix homogeneously; The weight ratio of EC and BL is EC:BL=3:7, adds electric conducting lithium salt LiPF afterwards6So that it is concentration in organic solvent is 1mol/L, mix homogeneously, stands.
Comparative example 3
At full argon (H2O < 10ppm, O2< 10ppm) glove mutually in, by organic solvent ethylene carbonate (EC), dimethyl carbonate (DMC) mix homogeneously; The weight ratio of EC and DMC is EC:DMC=3:7, adds electric conducting lithium salt LiPF afterwards6So that it is concentration in organic solvent is 0.8mol/L, is finally separately added into trimethyl phosphate (TMP), and consumption is 5wt.%; Vinylene carbonate (VC), consumption is 1wt.%, mix homogeneously, stands.
Above-described embodiment and comparative example are carried out combustion test test, and combustion test is as follows: the ceramic fiber paper that 5mm is thick is cut into the strip of 15 × 20mm size be placed in thermostatic drying chamber 85 DEG C dry 8 hours. Copper wire is cut into 10cm length, is hooked in top about 5mm place, ceramic fiber paper center, weigh the gross mass m of ceramic fiber paper and copper wire1, it is accurate to 0.01g. Ceramic fiber paper is put in 100ml beaker, pour electrolyte into and soak 5 minutes, take out ceramic fiber paper, weigh the gross mass m after soaking electrolyte with weight reduction2, it is accurate to 0.01g. The ceramic fiber paper soaking electrolyte is hung on iron stand, lights, record after burning things which may cause a fire disaster leaves to the time that ceramic fiber paper extinguishes, calculate self-extinguishing time:, test result is in Table 1.
When containing the high flash solvent of high level as can be seen from Table 1 in embodiment electrolyte, electrolyte is difficult to light, but self-extinguishing time is longer, and when containing high flash solvent in electrolyte with flame-retardant additive, electrolyte is difficult to light simultaneously, and self-extinguishing time is shorter simultaneously. The electrolyte of the present invention there is the characteristic being difficult to light and self-extinguishing time is shorter.
Claims (9)
1. a high security lithium ion battery electrolyte, it is characterized in that: electrolyte main component includes organic solvent, electrolyte and additive, including at least there being a kind of high flash solvent in described organic solvent, described additive includes film additive and flame-retardant additive.
2. the preparation method of a kind of high security lithium ion battery electrolyte as claimed in claim 1 and technology, it is characterised in that: electrolyte molar concentration in organic solvent is 0.8 ~ 1.5mol/L.
3. the preparation method of a kind of high security lithium ion battery electrolyte as claimed in claim 2 and technology, it is characterised in that: preferred electrolyte molar concentration in organic solvent is 1 ~ 1.2mol/L.
4. the preparation method of a kind of high security lithium ion battery electrolyte as claimed in claim 1 and technology, it is characterised in that: described high flash solvent is one or more in fluorinated solvents, sulfone kind solvent, cyclic carboxylic acids ester solvent.
5. the preparation method of a kind of high security lithium ion battery electrolyte as claimed in claim 4 and technology, it is characterized in that: described fluorinated solvents be preferably fluorinated ethylene carbonate (FEC), 1,1,2,2-tetra-fluoro ethyl-2,2,3,3-tetrafluoro propyl ethers etc., sulfone kind solvent is preferably sulfolane (TMS), dimethyl sulfite (DMS) etc., and cyclic carboxylic esters is preferably gamma-butyrolacton (BL).
6. the preparation method of a kind of high security lithium ion battery electrolyte as claimed in claim 1 and technology, it is characterised in that: in additive of the present invention, film for additive is: the one in vinylene carbonate, vinylethylene carbonate, fluorinated ethylene carbonate.
7. the preparation method of a kind of high security lithium ion battery electrolyte as claimed in claim 6 and technology, it is characterised in that: film for additive percetage by weight in the electrolytic solution is 1 ~ 2%.
8. the preparation method of a kind of high security lithium ion battery electrolyte as claimed in claim 1 and technology, it is characterised in that: described flame-retardant additive is the one in trimethyl phosphate, triphenyl phosphate, hexamethyl phosphine nitrile.
9. the preparation method of a kind of high security lithium ion battery electrolyte as claimed in claim 8 and technology, it is characterised in that: flame-retardant additive percetage by weight in the electrolytic solution is 5 ~ 8%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610047321.6A CN105680097A (en) | 2016-01-25 | 2016-01-25 | High-safety lithium-ion battery electrolyte solution |
| PCT/CN2016/084416 WO2017128580A1 (en) | 2016-01-25 | 2016-06-01 | Method and technique for preparing electrolyte solution for high-safety lithium ion battery |
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| CN201610047321.6A CN105680097A (en) | 2016-01-25 | 2016-01-25 | High-safety lithium-ion battery electrolyte solution |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106099188A (en) * | 2016-07-27 | 2016-11-09 | 芜湖凯尔电气科技有限公司 | Explosion-proof lithium-ion battery electrolytes |
| CN109088097A (en) * | 2018-10-25 | 2018-12-25 | 河南省法恩莱特新能源科技有限公司 | A kind of flame-retardant electrolyte of lithium-ion-power cell |
| CN109599592A (en) * | 2018-11-07 | 2019-04-09 | 上海交通大学 | A kind of secondary lithium-sulfur battery intrinsic safety electrolyte and preparation method thereof |
| CN114039091A (en) * | 2021-10-27 | 2022-02-11 | 武汉理工大学 | Flame-retardant electrolyte suitable for high-voltage lithium ion battery |
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| CN114300749A (en) * | 2021-12-30 | 2022-04-08 | 江苏卫蓝新能源电池有限公司 | Wide-temperature flame-retardant lithium ion battery electrolyte |
| CN116666761B (en) * | 2023-07-03 | 2024-02-06 | 常州千沐新能源有限公司 | Phosphate-based deep eutectic flame-retardant electrolyte, preparation method and lithium ion battery thereof |
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- 2016-01-25 CN CN201610047321.6A patent/CN105680097A/en active Pending
- 2016-06-01 WO PCT/CN2016/084416 patent/WO2017128580A1/en active Application Filing
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| CN114039091A (en) * | 2021-10-27 | 2022-02-11 | 武汉理工大学 | Flame-retardant electrolyte suitable for high-voltage lithium ion battery |
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| WO2017128580A1 (en) | 2017-08-03 |
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Application publication date: 20160615 |
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