CN110364764A - A kind of electrolyte and preparation method thereof for lithium ion battery - Google Patents
A kind of electrolyte and preparation method thereof for lithium ion battery Download PDFInfo
- Publication number
- CN110364764A CN110364764A CN201910669024.9A CN201910669024A CN110364764A CN 110364764 A CN110364764 A CN 110364764A CN 201910669024 A CN201910669024 A CN 201910669024A CN 110364764 A CN110364764 A CN 110364764A
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- Prior art keywords
- electrolyte
- ionic liquid
- volume fraction
- lithium ion
- lithium
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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
-
- 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
- H01M10/42—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
-
- 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
-
- 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
The present invention relates to lithium ion battery technologies, it is desirable to provide a kind of electrolyte and preparation method thereof for lithium ion battery.The electrolyte is made of ionic liquid, propene carbonate and ethylene carbonate double ion；In the electrolytic solution, double ion is 40~90% to the volume fraction of ionic liquid, and the volume fraction of propene carbonate is 5~30%, and the volume fraction of ethylene carbonate is 5~30%.The double ion used in the present invention inherently has lithium ion to ionic liquid, does not need additionally to add lithium salts when configuring electrolyte；With high thermal decomposition temperature, the safety of the thermal stability and lithium ion battery of electrolyte is improved.Operation of the present invention is simple, and step is few, does not generate toxic by-product, is suitable for large-scale production.
Description
Technical field
The present invention relates to the technology of lithium ion battery, in particular to a kind of electrolyte that can be used for lithium ion battery and its
Preparation method.
Background technique
Lithium ion battery is one of main new energy system of current social, is mainly made of anode, electrolyte, cathode,
Charge and discharge is realized in the movement of the insertion and deintercalation of positive and negative anodes and lithium ion between positive and negative anodes by lithium ion.Lithium
The appearance and application of ion battery, solve traditional fossil energy bring problem of environmental pollution and non-sustainable development is asked
Topic etc..Lithium ion battery has higher energy density compared to other secondary cells such as lead-acid accumulator, can be used for portable
Formula equipment, such as laptop, mobile phone etc..
Traditional electrolyte that lithium ion battery uses, the electrolyte of common such as ethers and carbonates, due to it
Low boiling point and burning point, thermal stability is inadequate, and lithium ion battery is caused to always exist safety problem, such as lithium ion battery uses
It is improper to be easy explosion on fire etc..In recent years, various electrolyte are developed for more efficient safe lithium ion battery.
Ionic liquid is a kind of ionic compound being made of zwitterion, and flowable liquid is presented at normal temperature, therefore
Also referred to as ionic liquid at room temperature.Ionic liquid boiling point generally with higher and thermal decomposition temperature and higher ion-conductance
The advantages that conductance and wide electrochemical window.The above advantage makes ionic liquid solve lithium ion battery using security issues side
Face can be applied.
Chinese invention patent CN105655637A reports a kind of ionic liquid for lithium ion battery, especially a kind of
The ionic liquid of diphenyl phosphonic acid quaternary ammonium salt or diphenyl phosphonic acid quaternary alkylphosphonium salt.The production method can carry out in batches, is at low cost；Make
It can ensure that lithium battery works at high temperature with the electrolyte of the production of the ionic liquid.When use diphenyl phosphonic acid methyl tributyl
When quaternary phosphonium salt ionic liquid electrolyte, lithium titanate material, battery initial discharge capacity reaches 170mAh/g, holds close to its theory
Amount.
Chinese invention patent CN105609878A reports a kind of composite electrolyte containing piperidines ionic liquid, can work as
Make high voltage electrolyte of lithium ion battery.The electrolyte includes lithium salts, piperidines ionic liquid, organic solvent and additive, tool
Have the features such as not volatile, nonflammable, high thermal stability, electrochemical window mouth width, good chemical stability, can 4.5V with
On high voltage under normal use.After the circle of circulating battery 200, capacity retention ratio is 80% or more.But the electrolyte system
Additional lithium salts, a variety of organic solvents, additive, complicated component need to be added.
Therefore, invent it is a kind of it is containing ionic liquid, can be effective for the electrolyte of lithium ion battery, for improving lithium ion
The security performance of battery is of great significance.
Summary of the invention
The technical problem to be solved by the present invention is to overcome deficiency in the prior art, providing one kind can be used for lithium-ion electric
The electrolyte in pond and preparation method thereof.
In order to solve the technical problem, solution of the invention is:
A kind of electrolyte for lithium ion battery is provided, which is by double ion to ionic liquid, propylene carbonate
Ester and ethylene carbonate composition；
Chemical structure of the double ion to ionic liquid are as follows:
In the electrolytic solution, double ion is 40~90% to the volume fraction of ionic liquid, the volume fraction of propene carbonate
It is 5~30%, the volume fraction of ethylene carbonate is 5~30%.
It is according to the volume invention further provides the preparation method for the electrolyte for being previously used for lithium ion battery
The proportionate relationship of score takes double ion to ionic liquid, propene carbonate and ethylene carbonate respectively, in the gloves of anhydrous and oxygen-free
It is uniformly mixed in case and obtains electrolyte.
Inventive principle description:
Ionic liquid boiling point with higher itself and thermal decomposition temperature can adapt to the extreme ring using lithium ion battery
Border.In addition ionic liquid has wider electrochemical window, and chemistry is still able to maintain in lithium ion battery charge and discharge process
Property is stable and electrochemical properties are stablized.The organic matter that carbonates are added in ionic liquid, can improve single ionic liquid
Body is used for charge-discharge performance not ideal enough disadvantage when lithium ion battery, while the addition of ionic liquid, can also improve electricity
Solve the security performance of liquid.
Compared with prior art, the beneficial effects of the present invention are:
1, the double ion used in the present invention inherently has lithium ion to ionic liquid, does not need when configuring electrolyte
Additional addition lithium salts.
2, the double ion that the present invention uses has high thermal decomposition temperature to ionic liquid, improves the thermostabilization of electrolyte
The safety of property and lithium ion battery.
3, operation of the present invention is simple, and step is few, does not generate toxic by-product, is suitable for large-scale production.
Detailed description of the invention
Fig. 1 is the lithium/ferric phosphate lithium cell specific discharge capacity made of electrolyte of the invention and charge and discharge cycles
The relation curve of number.
Fig. 2 is thermal decomposition temperature of the double ion of the invention used to ionic liquid.
Specific embodiment
Present invention is further described in detail with specific embodiment with reference to the accompanying drawing；Following example can make this
The present invention, but do not limit the invention in any way is more fully understood in the professional technician of profession.
Preparation method of the double ion to ionic liquid in the present invention:
By 1 mole of three (3,6- dioxaheptyl) amine and 1 mole of 2- bromoethyl Sulfonic Lithium be dissolved in 880 ml deionized waters and
In the mixed solvent made of 176 milliliters of dehydrated alcohols is stirred at reflux 72 hours under 100 DEG C of oil bath.Then revolving removes water
And dehydrated alcohol.750 milliliters of water are added, are then extracted with dichloromethane three times, every time with 750 milliliters of methylene chloride, stay water phase
Product.The water that water-phase product removes methylene chloride and 80% is rotated, 1 mole of lithium perchlorate is then added, is stirred 6 hours, is stood
After filter, rotary evaporation remove water, in a vacuum drying oven dry 24 hours to get to double ion to ionic liquid.This pair from
Son is 178 DEG C to the thermal decomposition temperature of ionic liquid.
Chemical structure of the double ion prepared to ionic liquid are as follows:
Embodiment 1
By 4.0 milliliters of double ions to ionic liquid, 3.0 milliliters of ethylene carbonates and 3.0 milliliters of propene carbonates anhydrous
It is uniformly mixed in the glove box of anaerobic and is configured to electrolyte.The electrolyte is used to assemble button lithium/ferric phosphate lithium cell, to institute
Obtain the charge-discharge test under battery progress 0.5C.
In the electrolyte obtained by the present embodiment, volume fraction shared by propene carbonate is 30%, shared by ethylene carbonate
Volume fraction be 30%, double ion to volume fraction shared by ionic liquid be 40%.
Embodiment 2
By 8.0 milliliters of double ions to ionic liquid, 0.5 milliliter of ethylene carbonate and 1.5 milliliters of propene carbonates anhydrous
It is uniformly mixed in the glove box of anaerobic and is configured to electrolyte.The electrolyte is used to assemble button lithium/ferric phosphate lithium cell, to institute
Obtain the charge-discharge test under battery progress 0.5C.
In the electrolyte obtained by the present embodiment, volume fraction shared by propene carbonate is 15%, shared by ethylene carbonate
Volume fraction be 5%, double ion to volume fraction shared by ionic liquid be 80%.
Embodiment 3
By 7.0 milliliters of double ions to ionic liquid, 1.5 milliliters of ethylene carbonates and 1.5 milliliters of propene carbonates anhydrous
It is uniformly mixed in the glove box of anaerobic and is configured to electrolyte.The electrolyte is used to assemble button lithium/ferric phosphate lithium cell, to institute
Obtain the charge-discharge test under battery progress 0.5C.
In the electrolyte obtained by the present embodiment, volume fraction shared by propene carbonate is 15%, shared by ethylene carbonate
Volume fraction be 15%, double ion to volume fraction shared by ionic liquid be 70%.
Embodiment 4
By 6.5 milliliters of double ions to ionic liquid, 3.0 milliliters of ethylene carbonates and 0.5 milliliter of propene carbonate anhydrous
It is uniformly mixed in the glove box of anaerobic and is configured to electrolyte.The electrolyte is used to assemble button lithium/ferric phosphate lithium cell, to institute
Obtain the charge-discharge test under battery progress 0.5C.
In the electrolyte obtained by the present embodiment, volume fraction shared by propene carbonate is 5%, shared by ethylene carbonate
Volume fraction is 30%, and double ion is 65% to volume fraction shared by ionic liquid.
Embodiment 5
By 8.0 milliliters of double ions to ionic liquid, 1.0 milliliters of ethylene carbonates and 1.0 milliliters of propene carbonates anhydrous
It is uniformly mixed in the glove box of anaerobic and is configured to electrolyte.The electrolyte is used to assemble button lithium/ferric phosphate lithium cell, to institute
Obtain the charge-discharge test under battery progress 0.5C.
In the electrolyte obtained by the present embodiment, volume fraction shared by propene carbonate is 10%, shared by ethylene carbonate
Volume fraction be 10%, double ion to volume fraction shared by ionic liquid be 80%.
Embodiment 6
By 9.0 milliliters of double ions to ionic liquid, 0.5 milliliter of ethylene carbonate and 0.5 milliliter of propene carbonate anhydrous
It is uniformly mixed in the glove box of anaerobic and is configured to electrolyte.The electrolyte is used to assemble button lithium/ferric phosphate lithium cell, to institute
Obtain the charge-discharge test under battery progress 0.5C.
In the electrolyte obtained by the present embodiment, volume fraction shared by propene carbonate is 5%, shared by ethylene carbonate
Volume fraction is 5%, and double ion is 90% to volume fraction shared by ionic liquid.
Embodiment 7
By 7.0 milliliters of double ions to ionic liquid, 1.0 milliliters of ethylene carbonates and 2.0 milliliters of propene carbonates anhydrous
It is uniformly mixed in the glove box of anaerobic and is configured to electrolyte.The electrolyte is used to assemble button lithium/ferric phosphate lithium cell, to institute
Obtain the charge-discharge test under battery progress 0.5C.
In the electrolyte obtained by the present embodiment, volume fraction shared by propene carbonate is 10%, shared by ethylene carbonate
Volume fraction be 20%, double ion to volume fraction shared by ionic liquid be 70%.
Embodiment 8
By 6.5 milliliters of double ions to ionic liquid, 0.5 milliliter of ethylene carbonate and 3.0 milliliters of propene carbonates anhydrous
It is uniformly mixed in the glove box of anaerobic and is configured to electrolyte.The electrolyte is used to assemble button lithium/ferric phosphate lithium cell, to institute
Obtain the charge-discharge test under battery progress 0.5C.
In the electrolyte obtained by the present embodiment, volume fraction shared by propene carbonate is 30%, shared by ethylene carbonate
Volume fraction be 5%, double ion to volume fraction shared by ionic liquid be 65%.
Embodiment 9
By 8.5 milliliters of double ions to ionic liquid, 0.5 milliliter of ethylene carbonate and 1.0 milliliters of propene carbonates anhydrous
It is uniformly mixed in the glove box of anaerobic and is configured to electrolyte.The electrolyte is used to assemble button lithium/ferric phosphate lithium cell, to institute
Obtain the charge-discharge test under battery progress 0.5C.
In the electrolyte obtained by the present embodiment, volume fraction shared by propene carbonate is 10%, shared by ethylene carbonate
Volume fraction be 5%, double ion to volume fraction shared by ionic liquid be 85%.
The relationship of button lithium/ferric phosphate lithium cell specific discharge capacity and charge and discharge cycles number in embodiment 6,9 is bent
Line is as shown in Figure 1.
Comparative example 1
8 milliliters of ethylene carbonates and 2 milliliters of propene carbonates are uniformly mixed in the glove box of anhydrous and oxygen-free and are configured to
Electrolyte.The electrolyte is used to assemble button lithium/ferric phosphate lithium cell, the charge and discharge electrical measurement under 0.5C is carried out to gained battery
Examination.
In the electrolyte obtained by the present embodiment, volume fraction shared by propene carbonate is 20%, shared by ethylene carbonate
Volume fraction be 80%.
Comparative example 2
3 milliliters of ethylene carbonates and 7 milliliters of propene carbonates are uniformly mixed in the glove box of anhydrous and oxygen-free and are configured to
Electrolyte.The electrolyte is used to assemble button lithium/ferric phosphate lithium cell, the charge and discharge electrical measurement under 0.5C is carried out to gained battery
Examination.
In the electrolyte obtained by the present embodiment, volume fraction shared by propene carbonate is 70%, shared by ethylene carbonate
Volume fraction be 30%.
Button lithium/ferric phosphate lithium cell putting when recycling the 1st and 100 circle in 1. embodiment 6,9 of table and comparative example 1,2
Electric specific capacity and coulombic efficiency.
From table 1 it follows that button lithium/ferric phosphate lithium cell in embodiment 6,9 and comparative example 1,2 is in circulation the 1st
With when 100 circle specific discharge capacity and coulombic efficiency all relatively, it was demonstrated that electrolyte of the invention is in lithium/LiFePO4 electricity
Pond is applicatory.
Finally it should be noted that the above enumerated are only specific embodiments of the present invention.It is clear that the invention is not restricted to
Above embodiments can also have many variations.Those skilled in the art can directly lead from present disclosure
Out or all deformations for associating, it is considered as protection scope of the present invention.
Claims (2)
1. a kind of electrolyte for lithium ion battery, which is characterized in that the electrolyte is by double ion to ionic liquid, carbonic acid
Acrylic ester and ethylene carbonate composition；
Chemical structural formula of the double ion to ionic liquid are as follows:
In the electrolytic solution, double ion is 40~90% to the volume fraction of ionic liquid, the volume fraction of propene carbonate is 5~
30%, the volume fraction of ethylene carbonate is 5~30%.
2. the preparation method described in claims 1 for the electrolyte of lithium ion battery, which is characterized in that according to the volume
The proportionate relationship of score takes double ion to ionic liquid, propene carbonate and ethylene carbonate respectively, in the gloves of anhydrous and oxygen-free
It is uniformly mixed in case, obtains electrolyte.
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| CN201910669024.9A CN110364764A (en) | 2019-07-23 | 2019-07-23 | A kind of electrolyte and preparation method thereof for lithium ion battery |
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| CN201910669024.9A CN110364764A (en) | 2019-07-23 | 2019-07-23 | A kind of electrolyte and preparation method thereof for lithium ion battery |
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Application publication date: 20191022 |