CN108155416A - A kind of low temperature high-voltage lithium-ion battery electrolyte - Google Patents
A kind of low temperature high-voltage lithium-ion battery electrolyte Download PDFInfo
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- CN108155416A CN108155416A CN201711421935.7A CN201711421935A CN108155416A CN 108155416 A CN108155416 A CN 108155416A CN 201711421935 A CN201711421935 A CN 201711421935A CN 108155416 A CN108155416 A CN 108155416A
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- Prior art keywords
- electrolyte
- lithium
- low temperature
- ion battery
- additive
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Classifications
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
-
- 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
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
-
- 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
Abstract
A kind of low temperature high-voltage lithium-ion battery electrolyte, belongs to field of lithium ion battery.Including lithium salts, organic solvent and film for additive, it is characterised in that：By the way that lithium salts and organic solvent are mixed to form electrolyte system, then add in film for additive and be made, the lithium salts is LiBF4With LiODFB mixtures, wherein LiBF4Molar ratio with LiODFB is 9：1~1：9, organic solvent includes ethylene carbonate and methyl ethyl ester, and ethylene carbonate and methyl ethyl ester volume ratio are 1：2.5 ~ 4, lithium salt is 0.9 ~ 1.2mol/L in the electrolyte system, and film for additive is fluorinated ethylene carbonate, and film for additive dosage is the 1 ~ 6% of electrolyte gross mass.The electrolyte is suitable for high-voltage battery, and the high-voltage battery of preparation has excellent cycle performance, and with excellent resistance to low temperature.
Description
Technical field
A kind of low temperature high-voltage lithium-ion battery electrolyte, belongs to field of lithium ion battery.
Background technology
With application of the lithium ion battery in fields such as electric vehicle, military affairs, aviations, to the energy density of lithium ion battery
Propose higher requirement.Other than the manufacture craft to current material and battery is improved, high-voltage anode material is
Compare one of popular research direction, it is to realize that the high-energy of battery is close by promoting the depth of charge of positive electrode active materials
Degree.However oxygenolysis can occur under the voltage of 4.5 ~ 5V for the carbonates electrolyte of traditional lithium-ion battery, cause lithium from
For the efficiency for charge-discharge of sub- battery than relatively low, cycle performance is poor, constrains the further development of high-voltage lithium ion batteries.
For the research direction of high pressure resistant electrolyte, first, novel high voltage solvent is developed, such as nitrile, sulfone class, ionic liquid
Body etc., second is that in LiPF6High voltage withstanding or film for additive is added in base carbonic ester electrolyte system.Numerous studies show newly
The exploitation of type high voltage dicyandiamide solution and use cost are higher, it is often more important that nitrile solvents and sulfone class solvent and graphite cathode
Compatibility can not show a candle to conventional carbonate-based solvent, molten so as to cause there is no novel dissolvent that can substitute conventional carbonates completely at present
Agent.Therefore, the numerous studies of high-voltage electrolyte are concentrated on by adding in the conventional carbonate-based solvent system of additive improvement at present.
From the point of view of the research of open report, in terms of the exploitation of high-voltage electrolyte, introducing high pressure additive can generally obtain
Obtain the electrolyte of 4.4 ~ 4.5 V.But for positive electrodes such as rich lithium, phosphoric acid vanadium lithium, high pressure nickel manganese, due to chargeable voltage
4.8 V even 5 more than V are reached, it is necessary to which the electrolyte that exploitation is resistant to higher voltage could obtain higher energy density.
In addition, the application range of lithium ion battery is constantly expanded in recent years, to the temperature limit of lithium ion battery
Propose the offline limitation of higher requirement, especially low temperature.Battery energy density declines to a great extent under cryogenic, therefore opens
It is imperative to send out high voltage bearing electrolyte under low temperature.
The LiPF of existing commercialization6Base carbonic ester electrolyte system, LiPF6Though dissolubility is good in organic solvent, have higher
Conductivity, but its decomposition temperature is relatively low, and thermal stability is very poor, is extremely easy in decomposition under high temperature, and extremely sensitive to water, is also easy to produce HF
Corroding electrode causes cycle performance of battery to decline；Part carbonate solvent there are viscosity under fusing point high and low temperature it is big the deficiencies of make electricity
Decline suddenly, and in high-voltage battery system under solution liquid conductivity low temperature, carbonic ester electrolyte is low because of oxidation-stabilized current potential
Oxygenolysis easily occurs in 4.5V, and causes hydraulic performance decline under battery low-temperature/high-pressure.
Invention content
The technical problem to be solved by the present invention is to：It overcomes the deficiencies of the prior art and provide a kind of low temperature resistant and high voltage bearing
Lithium-ion battery electrolytes, the electrolyte are suitable for high-voltage battery, and the high-voltage battery of preparation has excellent cycle performance,
And with excellent resistance to low temperature.
The technical solution adopted by the present invention to solve the technical problems is：The low temperature high-voltage lithium-ion battery electrolyte,
Including lithium salts, organic solvent and film for additive, it is characterised in that：By the way that lithium salts and organic solvent are mixed to form electrolyte
Then system adds in film for additive and is made, the lithium salts is LiBF4With LiODFB mixtures, wherein LiBF4With rubbing for LiODFB
You are than being 9：1~1：9, organic solvent includes ethylene carbonate and methyl ethyl ester, ethylene carbonate and methyl ethyl
Ester volume ratio is 1：2.5 ~ 4, lithium salt is 0.9 ~ 1.2mol/L in the electrolyte system, and film for additive is fluoro carbonic acid
Vinyl acetate, film for additive dosage are the 1 ~ 6% of electrolyte gross mass.
Preferably, the LiBF4Molar ratio with LiODFB is 8：2~3：7.
The organic solvent further includes propene carbonate, propene carbonate, ethylene carbonate and methyl ethyl ester body
Product is than being 1：0.5~1.5：2.5~3.5.
Preferably, the propene carbonate, ethylene carbonate and methyl ethyl ester volume ratio are 1：1：3.
Preferably, lithium salt is 1mol/L in the electrolyte system.
Preferably, the film for additive dosage is the 5% of electrolyte gross mass.
Technical scheme of the present invention mainly improves the electrification of electrolyte by using mixing lithium salts and film for additive
Learn performance.LiBF4Thermal stability is high, insensitive to water, low-temperature charge transfger impedance is small, is suitble to low temperature and high-multiplying power discharge, but
It is LiBF4Filming performance is bad, and LiODFB overcomes LiBF4The shortcomings that conductivity is low, filming performance is poor, can be in positive electrode surface
Film forming, reduces catalytic action of the active site to electrolyte decomposition of positive electrode surface, makes electrolysis liquid energy close to itself theoretical oxygen
It works under conditions of change decomposition voltage.
Using fluoro carbonic ester class additive, since fluorine atom has strong electronegativity and low pole, fluoride is caused to have
Stronger electrochemical stability, while fluorinated ethylene carbonate（FEC）Stable SEI films can be formed in negative terminal surface, are prevented molten
Destruction of the insertion of agent lithium ion to negative material.Mixing lithium salts and additive are used cooperatively, and are generated synergistic function, are made
Electrolyte can use under low temperature/high voltage condition, effectively improve the high voltage capability of battery.
Compared with prior art, advantageous effect possessed by the present invention is：
1st, the LiBF of certain mol proportion is selected in the present invention4With LiODFB as mixing lithium salts, organic solvent includes ethylene carbonate
Ester（EC）With methyl ethyl ester（EMC）, the synergistic effect of the two improves the cryogenic property and high-voltage stability of electrolyte
Can, in addition fluorinated ethylene carbonate as additive with good filming performance, can negative terminal surface formed it is form compact and stable,
Low-impedance SEI films enhance electrolyte oxidative resistance and reduce electrolyte surface tension, ensure that high-voltage anode material and electricity
The good interface compatibility of liquid is solved, the high-voltage battery of preparation has excellent cycle performance, under 4.9V high pressures, during room temperature
First discharge specific capacity reaches 110.9 ~ 129.5 mAh/g, and capacity retention ratio reaches 84.3 ~ 96.1 after recycling 300 weeks.
2nd, the present invention uses mixing lithium salts LiBF4And LiODFB, combine LiBF4Impedance is small under low temperature, low temperature performance well and
LiODFB stability is good, easy film forming, the advantages of conductivity is high, while preferably suitable lithium salts proportioning, the collaboration effect both played
Should, the electrolyte system of structure has excellent low temperature/high voltage capability, under the conditions of -20 DEG C, battery first discharge specific capacity
Reach 90.5 ~ 104.4 mAh/g, and capacity retention ratio reaches 82.9 ~ 97.2 after recycling 200 weeks.
Description of the drawings
Fig. 1 is electrolyte battery normal-temperature circulating performance figure prepared by embodiment 1 ~ 8 and comparative example 1 ~ 7.
Fig. 2 is electrolyte battery low-temperature circulating performance map prepared by embodiment 1 ~ 8 and comparative example 1 ~ 7.
Specific embodiment
With reference to embodiment, the present invention will be further described, and embodiment 1 is most preferred embodiment.
Component used is LITHIUM BATTERY in embodiment and comparative example.
Table 1 show each component dosage in electrolyte prepared by embodiment 1 ~ 8 and comparative example 1 ~ 7
Preparation process includes the following steps：
1）In the glove box full of argon gas, by LiBF4It is dissolved separately in organic solvent after being weighed with LiODFB, stirring makes lithium
Salt all dissolves, and forms electrolyte system；
2）FEC is added in above-mentioned electrolyte system, is uniformly mixed, sealing is placed in glove box 24 hours, spare.
Performance test：Cycle performance is carried out after electrolyte prepared by embodiment 1 ~ 8 and comparative example 1 ~ 7 is distinguished assembled battery
Test, method are as follows：Using nickel ion doped as anode, lithium piece is cathode, and aluminium foil is collector, diaphragm using Celgard 2400 every
Film assembles button half-cell in glove box, is tested after standing 12h.It is arrived under 25 °C of constant temperature of room temperature with 1/10C 2.8V
4.9V carries out charge and discharge and battery is activated, then respectively under the conditions of -20 °C and 25 °C of room temperature with 1/10C and 1C charge and discharge
Cycle, test result are shown in Table 2.
The electric discharge for the first time of battery prepared by 2 embodiment 1 ~ 8 of table and 1 ~ 7 electrolyte of comparative example under the conditions of 25 DEG C and -20 DEG C
Specific capacity and conservation rate test result.
As shown in Table 2, LiBF is selected4With LiODFB mixtures as lithium salts, with reference to PC, EC and EMC as organic solvent,
The electrolyte that FEC is prepared as film for additive has apparent high voltage performance, under 4.9V high pressures, putting for the first time during room temperature
Electric specific capacity reaches 110.9 ~ 129.5 mAh/g, hence it is evident that higher than 96.5 ~ 102.2 mAh/g of comparative example, and recycles 300 weeks
Capacity retention ratio reaches 84.3 ~ 96.1 afterwards, far above comparative example 21.4 ~ 39.6%；Meanwhile under the conditions of -20 DEG C, battery is for the first time
Specific discharge capacity reaches 90.5 ~ 104.4 mAh/g, hence it is evident that higher than 61.3 ~ 81.8 mAh/g of comparative example, and recycles 200 weeks
Capacity retention ratio reaches 82.9 ~ 97.2 afterwards, hence it is evident that higher than comparative example 1 ~ 7；Illustrate that the electrolyte of the present invention is suitable for high-tension battery
In, and with excellent resistance to low temperature.
The above described is only a preferred embodiment of the present invention, being not that the invention has other forms of limitations, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But it is every without departing from technical solution of the present invention content, technical spirit according to the present invention is to above example institute
Any simple modification, equivalent variations and the remodeling made still fall within the protection domain of technical solution of the present invention.
Claims (6)
1. a kind of low temperature high-voltage lithium-ion battery electrolyte, including lithium salts, organic solvent and film for additive, feature exists
In：By the way that lithium salts and organic solvent are mixed to form electrolyte system, then add in film for additive and be made, the lithium salts is
LiBF4With LiODFB mixtures, wherein LiBF4Molar ratio with LiODFB is 9：1~1：9, organic solvent includes ethylene carbonate
With methyl ethyl ester, ethylene carbonate and methyl ethyl ester volume ratio are 1：2.5 ~ 4, lithium in the electrolyte system
Salinity is 0.9 ~ 1.2mol/L, and film for additive is fluorinated ethylene carbonate, and film for additive dosage is electrolyte gross mass
1 ~ 6%.
2. low temperature high-voltage lithium-ion battery electrolyte according to claim 1, it is characterised in that：The LiBF4With
The molar ratio of LiODFB is 8：2~3：7.
3. low temperature high-voltage lithium-ion battery electrolyte according to claim 1, it is characterised in that：The organic solvent is also
Including propene carbonate, propene carbonate, ethylene carbonate and methyl ethyl ester volume ratio are 1：0.5~1.5：2.5~
3.5。
4. low temperature high-voltage lithium-ion battery electrolyte according to claim 3, it is characterised in that：The propylene carbonate
Ester, ethylene carbonate and methyl ethyl ester volume ratio are 1：1：3.
5. low temperature high-voltage lithium-ion battery electrolyte according to claim 1, it is characterised in that：The electrolyte system
Middle lithium salt is 1mol/L.
6. low temperature high-voltage lithium-ion battery electrolyte according to claim 1, it is characterised in that：The film for additive
Dosage is the 5% of electrolyte gross mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711421935.7A CN108155416A (en) | 2017-12-25 | 2017-12-25 | A kind of low temperature high-voltage lithium-ion battery electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711421935.7A CN108155416A (en) | 2017-12-25 | 2017-12-25 | A kind of low temperature high-voltage lithium-ion battery electrolyte |
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| Publication Number | Publication Date |
|---|---|
| CN108155416A true CN108155416A (en) | 2018-06-12 |
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| CN201711421935.7A Pending CN108155416A (en) | 2017-12-25 | 2017-12-25 | A kind of low temperature high-voltage lithium-ion battery electrolyte |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110635166A (en) * | 2018-06-21 | 2019-12-31 | 比亚迪股份有限公司 | Electrolyte, battery containing electrolyte and electric vehicle |
| CN114583162A (en) * | 2020-12-02 | 2022-06-03 | 天津理工大学 | Application of tripyridyl multidirectional polycarboxylic acid compound and low-temperature battery thereof |
-
2017
- 2017-12-25 CN CN201711421935.7A patent/CN108155416A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110635166A (en) * | 2018-06-21 | 2019-12-31 | 比亚迪股份有限公司 | Electrolyte, battery containing electrolyte and electric vehicle |
| CN114583162A (en) * | 2020-12-02 | 2022-06-03 | 天津理工大学 | Application of tripyridyl multidirectional polycarboxylic acid compound and low-temperature battery thereof |
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| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180612 |
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| WD01 | Invention patent application deemed withdrawn after publication |