CN107171023A - A kind of low temperature electrolytes for Li-ion batteries - Google Patents
A kind of low temperature electrolytes for Li-ion batteries Download PDFInfo
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- CN107171023A CN107171023A CN201710348186.3A CN201710348186A CN107171023A CN 107171023 A CN107171023 A CN 107171023A CN 201710348186 A CN201710348186 A CN 201710348186A CN 107171023 A CN107171023 A CN 107171023A
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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
- 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
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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
- H01M10/0568—Liquid materials characterised by the solutes
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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
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
- H01M2300/0042—Four or more solvents
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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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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The present invention relates to a kind of low temperature electrolytes for Li-ion batteries, solvent and solute two parts are included；It is characterized in that：Solvent is made up of ethylene carbonate, dimethyl carbonate, fluoropropylene carbonate and chlorocarbonic acid propylene, and the volume ratio of four kinds of materials is VEC：VDMC：VF‑PC：VCl‑PC=（45~49）：（45~49）：（1~5）：（1~7）；Solute is by LiPF6And LiBF4Constitute, the mass ratio of two kinds of materials is mLiPF6：mLiBF4=（7.5~9）：1；The overall density of electrolyte is 0.8 ~ 1.5mol/L.Specific electrolyte configuration can be carried out in glove box, after being weighed respectively to solvent and solute, be placed in container, well mixed by modes such as convention stir, concussion, ultrasounds.Using the PC materials replaced by the use of two kinds of halogens as electrolyte solute, PC inlay effect is solved；Electrolyte fusing point is reduced, electrolyte stability is improved, makes the low-temperature characteristics and security performance of electrolyte more outstanding.
Description
Technical field
The present invention relates to a kind of low temperature electrolytes for Li-ion batteries, belong to technical field of lithium ion.
Background technology
This energy storage device of lithium ion battery was widely cognitive by people in the last few years, and had also obtained preferably should
With in particular with the fast development of new-energy automobile, lithium battery technology, which there has also been, quickly to be improved and progressive.However, lithium from
Several problems that sub- battery still have do not find effective solution yet so far, such as the raising of energy density, the improvement of security performance,
Lifting of cryogenic property etc..Particularly the poor low-temperature characteristics of lithium battery, seriously constrains its development.For northern China
Speech, the lifting of the cryogenic property of lithium ion battery is more particularly important.
The factor of influence lithium battery cryogenic property has a lot, includes species, the component of electrolyte, the system of positive and negative electrode material
Make technique etc..Wherein electrolyte is to influence the most important factor of lithium battery cryogenic property, this is because, electrolyte during low temperature
Viscosity becomes big, ion and electronic conductivity step-down, and the ion-transfer between both positive and negative polarity receives limitation, the activity reduction of battery.Pin
General solution to electrolyte poor performance at low temperatures has：（1）Special additive is added in the electrolytic solution, reduces its fusing point；（2）
Solvent composition is adjusted, changes electrolyte attribute；（3）Use new solute（Lithium salts）.However, above-mentioned measure is to battery cryogenic property
Raising it is also relatively limited.
It is well known that propene carbonate（PC）A kind of very outstanding low-temperature electrolyte solvent, it have fusing point it is low,
The advantages of boiling point height, wide operating temperature range and wide electrochemical window.Consider in terms of security, cryogenic property and price,
Its compatibility with positive electrode is good.However, the poor compatibility of PC molecules and graphite negative electrodes material, easily together with lithium ion
Embedded graphite layers, cause the structure leafing of graphite material.In order to which PC is used for lithium ion battery, the conventional selection of people is profit
Suppress the inlay reaction of PC molecules with different additive.Although such method inhibits the inlay effect of PC molecules, but
Excessive other materials are introduced in the electrolytic solution, excessive side reaction is easily produced, and the security to battery causes certain prestige
The side of body.
The content of the invention
The present invention be directed to lithium ion battery poor performance at low temperatures the problem of there is provided a kind of low temperature electrolytes for Li-ion batteries,
Using the PC materials replaced by the use of two kinds of halogens as electrolyte solute, PC inlay effect is solved；The low temperature electrolytic solution has molten
Matter and solvent two parts are constituted, and wherein solute is binary system, by LiPF6And LiBF4Constitute, solvent is quaternary system, by carbonic acid
Vinyl acetate（EC）, dimethyl carbonate（DMC）, fluoropropylene carbonate（F-PC）With chlorocarbonic acid propylene（Cl-PC）Constitute, drop
Low electrolyte fusing point, improves electrolyte stability, makes the low-temperature characteristics and security performance of electrolyte more outstanding.
The technical proposal of the invention is realized in this way：A kind of low temperature electrolytes for Li-ion batteries, includes solvent and solute
Two parts；It is characterized in that：Solvent is by ethylene carbonate, dimethyl carbonate, fluoropropylene carbonate and chlorocarbonic acid propylene
Constitute, the volume ratio of four kinds of materials is VEC：VDMC：VF-PC：VCl-PC=（45~49）：（45~49）：（1~5）：（1~7）；Solute by
LiPF6And LiBF4Constitute, the mass ratio of two kinds of materials is mLiPF6：mLiBF4=（7.5~9）：1；The overall density of electrolyte is
0.8~1.5mol/L.Specific electrolyte configuration can be carried out in glove box, after being weighed respectively to solvent and solute, be placed on appearance
It is well mixed by modes such as convention stir, concussion, ultrasounds in device.
The positive effect of the present invention is：（1）Electrolyte solvent is used as by the use of the chlorocarbonic acid propylene with large-size
One of, the inlay for reducing PC molecules in GND graphite reacts, and reduces electrolyte fusing point, improves electrolyte low-temperature characteristics；（2）
Fluoropropylene carbonate is added with electrolyte, solvent and solute is improved（LiPF6）Compatibility（F-, similar compatibility）.Meanwhile,
Fluoropropylene carbonate molecular dimension is also larger, can equally suppress inlay reaction；（3）Due to LiBF4With low temperature performance well,
The good advantage of heat endurance, in LiPF6A small amount of LiBF is added in solute4Material can improve the low-temperature characteristics and peace of electrolyte
Omnicharacteristic；（4）Lithium battery low temperature performance well, the security that the low-temperature electrolyte provided using the present invention is made are good, and particularly three
The lithium battery of first positive pole system.
Brief description of the drawings
Fig. 1 is lithium ion battery in present example 1-30oDischarge curve at a temperature of C.
Embodiment
The invention will be further described with embodiment below in conjunction with the accompanying drawings：
Embodiment 1
By ethylene carbonate, dimethyl carbonate, fluoropropylene carbonate and chlorocarbonic acid propylene by volume 45：45：3：7 mix
Close, form electrolyte solvent after stirring, then by LiPF6And LiBF4In mass ratiom LiPF6：m LiBF4=8：It is molten after 1 ratio mixing
In in above-mentioned solvent, in glove box after strong stirring, it can be configured to the low-temperature electrolyte that concentration is 1.2mol/L.Use the electricity
The lithium ion soft-package battery cryogenic property that solution liquid, ternary NCM811 positive poles are fabricated to is outstanding, as a result as shown in table 1.
Embodiment 2
By ethylene carbonate, dimethyl carbonate, fluoropropylene carbonate and chlorocarbonic acid propylene by volume 45：49：5：1 mixes
Close, form electrolyte solvent after stirring, then by LiPF6And LiBF4In mass ratiom LiPF6：m LiBF4=7.5：After 1 ratio mixing
It is dissolved in above-mentioned solvent, in glove box after strong stirring, can be configured to the low-temperature electrolyte that concentration is 0.8 mol/L.
Embodiment 3
By ethylene carbonate, dimethyl carbonate, fluoropropylene carbonate and chlorocarbonic acid propylene by volume 49：45：1：5 mix
Close, form electrolyte solvent after stirring, then by LiPF6And LiBF4In mass ratiom LiPF6：m LiBF4=8：It is molten after 1 ratio mixing
In in above-mentioned solvent, in glove box after strong stirring, it can be configured to the low-temperature electrolyte that concentration is 1.5mol/L.
Embodiment 4
By ethylene carbonate, dimethyl carbonate, fluoropropylene carbonate and chlorocarbonic acid propylene by volume 47：47：4：6 mix
Close, form electrolyte solvent after stirring, then by LiPF6And LiBF4In mass ratiom LiPF6：m LiBF4=8.5：After 1 ratio mixing
It is dissolved in above-mentioned solvent, in glove box after strong stirring, can be configured to the low-temperature electrolyte that concentration is 1.2mol/L.Use this
The lithium ion soft-package battery cryogenic property that electrolyte, ternary NCM811 positive poles are fabricated to is outstanding, as a result as shown in table 1.
Under the different temperatures of table 1 in example 1 lithium ion battery low-temperature characteristics.
Claims (1)
1. a kind of low temperature electrolytes for Li-ion batteries, includes solvent and solute two parts；It is characterized in that：Solvent is by ethylene carbonate
Ester, dimethyl carbonate, fluoropropylene carbonate and chlorocarbonic acid propylene are constituted, and the volume ratio of four kinds of materials is VEC：VDMC：
VF-PC：VCl-PC=（45~49）：（45~49）：（1~5）：（1~7）；Solute is by LiPF6And LiBF4Constitute, the mass ratio of two kinds of materials
For mLiPF6：mLiBF4=（7.5~9）：1；The overall density of electrolyte is 0.8 ~ 1.5mol/L；Specific electrolyte configuration can be
Carried out in glove box, after being weighed respectively to solvent and solute, be placed in container, pass through the modes such as convention stir, concussion, ultrasound
It is well mixed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710348186.3A CN107171023A (en) | 2017-05-17 | 2017-05-17 | A kind of low temperature electrolytes for Li-ion batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710348186.3A CN107171023A (en) | 2017-05-17 | 2017-05-17 | A kind of low temperature electrolytes for Li-ion batteries |
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| Publication Number | Publication Date |
|---|---|
| CN107171023A true CN107171023A (en) | 2017-09-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710348186.3A Pending CN107171023A (en) | 2017-05-17 | 2017-05-17 | A kind of low temperature electrolytes for Li-ion batteries |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109560324A (en) * | 2018-12-05 | 2019-04-02 | 江西赛特新能源科技有限公司 | A kind of resistance to super-low-temperature lithium-ion cell electrolyte |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102403535A (en) * | 2011-12-01 | 2012-04-04 | 香河昆仑化学制品有限公司 | Non-water electrolyte for high-voltage lithium ion battery and preparation method |
| CN103647110A (en) * | 2013-12-06 | 2014-03-19 | 华瑞(新乡)化工有限公司 | Ultralow temperature discharge electrolyte of novel lithium ion battery |
| 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 |
| CN106159329A (en) * | 2016-08-31 | 2016-11-23 | 东莞市航盛新能源材料有限公司 | A kind of lithium titanate battery electrolyte and lithium titanate battery |
-
2017
- 2017-05-17 CN CN201710348186.3A patent/CN107171023A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102403535A (en) * | 2011-12-01 | 2012-04-04 | 香河昆仑化学制品有限公司 | Non-water electrolyte for high-voltage lithium ion battery and preparation method |
| CN103647110A (en) * | 2013-12-06 | 2014-03-19 | 华瑞(新乡)化工有限公司 | Ultralow temperature discharge electrolyte of novel lithium ion battery |
| 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 |
| CN106159329A (en) * | 2016-08-31 | 2016-11-23 | 东莞市航盛新能源材料有限公司 | A kind of lithium titanate battery electrolyte and lithium titanate battery |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109560324A (en) * | 2018-12-05 | 2019-04-02 | 江西赛特新能源科技有限公司 | A kind of resistance to super-low-temperature lithium-ion cell 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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