CN101442144A - Method for stabilizing color and luster, moisture and fluohydric acid content of non-aqueous electrolyte - Google Patents
Method for stabilizing color and luster, moisture and fluohydric acid content of non-aqueous electrolyte Download PDFInfo
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- CN101442144A CN101442144A CNA2009100006685A CN200910000668A CN101442144A CN 101442144 A CN101442144 A CN 101442144A CN A2009100006685 A CNA2009100006685 A CN A2009100006685A CN 200910000668 A CN200910000668 A CN 200910000668A CN 101442144 A CN101442144 A CN 101442144A
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- electrolytic solution
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a method for stabilizing the color and luster, the water content and the hydrofluoric acid content of a nonaqueous electrolyte at a high temperature of between 50 and 70 DEG C. The method is to add a silicon amine compound and a phosphorous acid ester compound into the nonaqueous electrolyte, wherein the addition of the silicon amine compound and the phosphorous acid ester compound is 0.01 to 3 percent of the weight of the electrolyte. The compounds can effectively inhibit increase of the water content and the hydrofluoric acid content of the electrolyte and maintain stable quality of the electrolyte.
Description
Technical field
The present invention relates to technical field of lithium ion, relate to the method for stabilizing color and lustre of non-aqueous electrolyte, moisture and fluohydric acid content especially.
Background technology
Electrolyte is the important component part of lithium ion battery, and it is the ion conductor that plays conduction between the battery positive and negative electrode, the performance of itself and influence the performance of battery to a great extent with the state of interface that both positive and negative polarity forms.Good non-aqueous electrolyte for lithium ion cell should possess following some requirement.(1) chemical stability is good, with both positive and negative polarity active material and collector (generally using aluminium foil and Copper Foil) in the battery chemical reaction does not take place; (2) electrochemical stability window is wide; (3) ionic conductivity height, electronic conductivity is low; (4) film forming characteristics is good, forms form compact and stable passivating film on the graphite cathode material surface; (5) temperature range suitable (boiling point height, fusing point low); (6) safety and low toxicity, non-environmental-pollution.
Variable color takes place with nonaqueous electrolytic solution in lithium ion battery easily when transporting and store, especially under 50 ℃ of environment, deposit the phenomenon that will darken in 12 hours, influences its result of use.The main cause that causes the nonaqueous electrolytic solution variable color is in storage and transport process, along with the increase of electrolyte moisture, lithium salts decompose to produce a large amount of hydrofluoric acid, reacts with the trace impurity of electrolyte itself to cause, in 50～70 ℃ of environment, quickened above-mentioned reaction especially, more easy to change.Therefore stable nonaqueous electrolytic solution moisture and fluohydric acid content under 50～70 ℃ suppress its variable color, have positive meaning for the nonaqueous electrolytic solution practical function.
Summary of the invention
The technical problem that the present invention solves is: stable nonaqueous electrolytic solution moisture and fluohydric acid content under 50～70 ℃, suppress its variable color.
The technical solution used in the present invention is, adds silicon aminated compounds and phosphite ester compound in nonaqueous electrolytic solution, and addition is 0.01%～3% of an electrolyte weight.
Above-mentioned nonaqueous electrolytic solution is: organic solvent and electric conducting lithium salt by carbonic ester and carboxylic acid esters are formed.
Carbonic ester is selected from least a or several in the following material: ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, diethyl carbonate, carbonic acid first butyl ester, ethyl butyl carbonate, dibutyl carbonate, chloro-ethylene carbonate, methyl ethyl carbonate, ethyl propyl carbonic acid ester, ethylene isopropyl ester, carbonic acid first propyl ester, carbonic acid first isopropyl ester.
Carboxylate is selected from least a or several in the following material: butyrolactone, valerolactone, caprolactone, methyl formate, Ethyl formate, ethyl acetate, propyl acetate, isopropyl acetate.
Above-mentioned silicon aminated compounds has following general structure:
R1～R7 is that carbon number is at least a in 0～12 the alkyl or aryl, and the carbon number of R1～R7 can not be zero simultaneously.R1～R7 can be the same or different.
Above-mentioned phosphite ester compound has following general structure:
R1, R2, R3 are that carbon number is at least a in 0～12 the alkyl or aryl, and R1～R3 carbon number can not be zero simultaneously.R1, R2, R3 can be the same or different.
Use method of the present invention, store 24～72 hours in 50 ℃～70 ℃ environment of high temperature, it is stable that nonaqueous electrolytic solution moisture and fluohydric acid content keep, and color and luster does not change.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Among the embodiment, the mensuration of moisture and hydrofluoric acid is measured with KarlFisher moisture teller and Karl Fisher potentiometric titrimeter respectively, and colourity adopts the GB/T3143-82 method to measure.
Embodiment 1
At the glove box of applying argon gas (preparation nonaqueous electrolytic solution 1M LiPF in the moisture＜5ppm)
6EC: DMC: EMC=1: 1: 1 (mass ratio), totally four parts, every part of 1L is a standard with the former state that does not contain additive, adds HMDS and tributyl phosphite 0.02%, 0.4%, 1% in its excess-three sample respectively, after the sealing, under 50 ℃ condition, compare test, detect the content and the color and luster of moisture and hydrofluoric acid, result such as following table.
As can be seen from the above table, add an amount of HMDS and tributyl phosphite in the nonaqueous electrolytic solution after, compare with un-added former state, it is stable that moisture and fluohydric acid content keep, color and luster is stable.
Embodiment 2
At the glove box of applying argon gas (preparation nonaqueous electrolytic solution 1M LiPF in the moisture＜5ppm)
6EC:DMC:EMC=1:1:1 (mass ratio), totally three parts, every part of 1L is a standard with the former state that does not contain additive, add 0.5% HMDS and tributyl phosphite in all the other two samples respectively, 0.5% Hexaethyl disilazane and triphenyl phosphite after the sealing, compare test under 50 ℃ condition, detect the content and the color and luster of moisture and hydrofluoric acid, result such as following table.
As can be seen from the above table, add an amount of silicon aminated compounds and phosphite ester compound in the nonaqueous electrolytic solution after, compare with un-added former state, it is stable that moisture and fluohydric acid content keep, color and luster is stable.
Embodiment 3
At the glove box of applying argon gas (preparation nonaqueous electrolytic solution 1M LiPF in the moisture＜5ppm)
6EC:DMC:EMC=1:1:1 (mass ratio), totally six parts, every part of 1L is standard (three parts) with the former state that does not contain additive, adds 0.3% HMDS and tributyl phosphite in its excess-three sample respectively, after the sealing, under 50 ℃～70 ℃ condition, compare test, detect the content and the color and luster of moisture and hydrofluoric acid, result such as following table.
As can be seen from the above table, after adding an amount of silicon aminated compounds and phosphite ester compound in the nonaqueous electrolytic solution, compare, in 50 ℃～70 ℃ environment of high temperature, store 72 hours with un-added former state, it is stable that moisture and fluohydric acid content keep, and color and luster does not change.
Claims (10)
1, the method for a kind of stabilizing color and lustre of non-aqueous electrolyte, moisture and fluohydric acid content is characterized in that: add silicon aminated compounds and phosphite ester compound.
2, method according to claim 1 is characterized in that: described silicon aminated compounds structural formula:
R1～R7 is that carbon number is at least a in 0～12 the alkyl or aryl, and R1～R7 carbon number can not be zero simultaneously.
3, method according to claim 1 is characterized in that: described phosphite ester compound structural formula:
R1, R2, R3 are that carbon number is at least a in 0～12 the alkyl or aryl, and R1～R3 carbon number can not be zero simultaneously.
4, method according to claim 1 is characterized in that: the addition of described silicon aminated compounds and phosphite ester compound is 0.01%～3% of an electrolyte weight.
5, method according to claim 1 is characterized in that: contain organic solvent carbonic ester and carboxylate in the described nonaqueous electrolytic solution.
6, method according to claim 5 is characterized in that: the organic solvent carbonic ester in the described nonaqueous electrolytic solution is selected from least a in the following material: ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, diethyl carbonate, carbonic acid first butyl ester, ethyl butyl carbonate, dibutyl carbonate, chloro-ethylene carbonate, methyl ethyl carbonate, ethyl propyl carbonic acid ester, ethylene isopropyl ester, carbonic acid first propyl ester, carbonic acid first isopropyl ester.
7, method according to claim 5 is characterized in that: the organic solvent carboxylate in the described nonaqueous electrolytic solution is selected from least a in the following material: butyrolactone, valerolactone, caprolactone, methyl formate, Ethyl formate, ethyl acetate, propyl acetate, isopropyl acetate.
8, method according to claim 1 is characterized in that: described nonaqueous electrolytic solution is the nonaqueous electrolytic solution that contains lithium salts.
9, method according to claim 8 is characterized in that: the lithium salts in the described nonaqueous electrolytic solution is a lithium hexafluoro phosphate.
10. non-water electrolytic solution additive that is used for lithium ion battery, it is characterized in that: additive is silicon aminated compounds and phosphite ester compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100006685A CN101442144A (en) | 2009-01-14 | 2009-01-14 | Method for stabilizing color and luster, moisture and fluohydric acid content of non-aqueous electrolyte |
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2009100006685A CN101442144A (en) | 2009-01-14 | 2009-01-14 | Method for stabilizing color and luster, moisture and fluohydric acid content of non-aqueous electrolyte |
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| CN101442144A true CN101442144A (en) | 2009-05-27 |
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| CNA2009100006685A Pending CN101442144A (en) | 2009-01-14 | 2009-01-14 | Method for stabilizing color and luster, moisture and fluohydric acid content of non-aqueous electrolyte |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102231445A (en) * | 2010-12-10 | 2011-11-02 | 北京化学试剂研究所 | Method for stabilizing chromaticity of lithium iodide non-aqueous electrolyte |
| CN102637901A (en) * | 2012-04-24 | 2012-08-15 | 广州市云通磁电有限公司 | Electrolyte for lithium ion battery and preparation method thereof |
| CN110600803A (en) * | 2019-09-05 | 2019-12-20 | 昆山宝创新能源科技有限公司 | Electrolyte for lithium battery and preparation method thereof |
| CN110718719A (en) * | 2018-07-13 | 2020-01-21 | 常熟理工学院 | Rechargeable zinc ion battery |
| CN114156526A (en) * | 2021-12-02 | 2022-03-08 | 浙江大学 | High-voltage electrolyte for lithium battery |
-
2009
- 2009-01-14 CN CNA2009100006685A patent/CN101442144A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102231445A (en) * | 2010-12-10 | 2011-11-02 | 北京化学试剂研究所 | Method for stabilizing chromaticity of lithium iodide non-aqueous electrolyte |
| CN102637901A (en) * | 2012-04-24 | 2012-08-15 | 广州市云通磁电有限公司 | Electrolyte for lithium ion battery and preparation method thereof |
| CN102637901B (en) * | 2012-04-24 | 2014-07-16 | 广州市云通磁电有限公司 | Electrolyte for lithium ion battery and preparation method thereof |
| CN110718719A (en) * | 2018-07-13 | 2020-01-21 | 常熟理工学院 | Rechargeable zinc ion battery |
| CN110718719B (en) * | 2018-07-13 | 2020-10-30 | 常熟理工学院 | Rechargeable zinc ion battery |
| CN110600803A (en) * | 2019-09-05 | 2019-12-20 | 昆山宝创新能源科技有限公司 | Electrolyte for lithium battery and preparation method thereof |
| CN114156526A (en) * | 2021-12-02 | 2022-03-08 | 浙江大学 | High-voltage electrolyte for lithium battery |
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Open date: 20090527 |