CN108417892A - A kind of ternary battery electrolytic solution and its preparation method - Google Patents
A kind of ternary battery electrolytic solution and its preparation method Download PDFInfo
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- CN108417892A CN108417892A CN201810101966.2A CN201810101966A CN108417892A CN 108417892 A CN108417892 A CN 108417892A CN 201810101966 A CN201810101966 A CN 201810101966A CN 108417892 A CN108417892 A CN 108417892A
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- ether
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- carbonate
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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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- 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 a kind of ternary battery electrolytic solution and its preparation method, the electrolyte is formulated by lithium salts, organic solvent, functional additive；Wherein, the functional additive is three (trimethyl silane) borates and 3,3', 5,5' tetramethyl benzidines.The preparation method is specially：At a temperature of 0 10 DEG C, lithium salts is added in organic solvent, after so that it is fully dissolved, adds three (trimethyl silane) borates and 3,3', 5,5' tetramethyl benzidines are to get the ternary battery electrolytic solution.The present invention passes through three (trimethyl silane) borates and 3,3', 5, the immixture of 5' tetramethyl benzidines, can effectively avoid ternary dynamic lithium battery, there is a phenomenon where voltage declines, fast, discharge capacity is insufficient in high-multiplying power discharge, to solve the problems, such as to perplex the ternary battery high-multiplying power discharge off-capacity of industry all the time.
Description
Technical field
The present invention relates to technical field of lithium batteries more particularly to a kind of ternary battery electrolytic solution and its preparation methods.
Background technology
Lithium battery is made of anode, cathode, diaphragm, four big material of electrolyte, lithium ion battery electrolyte be mostly liquid i.e.
Electrolyte.Electrolyte plays the role of conducting electronics between battery plus-negative plate, and the quality of electrolyte property will directly affect lithium
The comprehensive performance of ion battery.Since lithium ion battery charge and discharge potential is high, and anode is embedded with the larger lithium of chemism, therefore
Excellent electrolyte should meet claimed below：Chemical stability is good, ionic conductivity is high, temperature range is wide, safe and non-toxic etc..
Ternary battery is because it is with high-energy density, high working voltage, service life length, memory-less effect, course continuation mileage
The advantages that long, becomes focus of people's attention in recent years, in power battery field, the positive surging emergence of ternary battery.But charge and discharge
High rate performance restricts always the fast development of ternary battery, especially solves the problems, such as that high-multiplying power discharge off-capacity has become
The emphasis of industry research.
Invention content
The purpose of the present invention is to provide a kind of electrolyte of the promotion multiplying power discharging property of ternary battery, the electrolysis
Liquid is formulated by lithium salts, organic solvent, functional additive；Wherein, the functional additive is three (trimethyl silanes)
Borate and 3,3', 5,5'- tetramethyl benzidines.
Preferably, three (trimethyl silane) borate and 3,3', the sum of the weight of 5,5'- tetramethyl benzidines accounts for institute
State the 1%~10% of electrolyte weight；Preferably 4%~8%.
Preferably, three (trimethyl silane) borate and described 3,3', the weight ratio of 5,5'- tetramethyl benzidines are
0.5~2:1；Preferably 1:1.
Wherein, the organic solvent is one or more in ether solvent, esters solvent；
Preferably, the ether solvent is selected from ether, ethyl methyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol
It is one or more in dimethyl ether, tetraethyleneglycol dimethyl ether, ethylene glycol monoemethyl ether, dioxolane, dioxane；
The esters solvent is selected from propene carbonate, ethylene carbonate, butylene, dimethyl carbonate, carbonic acid diethyl
Ester, carbonic acid first butyl ester, ethyl butyl carbonate, dibutyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, chloroethylenes
It is one or more in carbonic ester, ethyl acetate, propyl acetate, ethyl propionate, methyl butyrate.
Preferably, the water content of the organic solvent is not higher than 10ppm.
When the organic solvent in the form of the mixed liquor of ether solvent and esters solvent to provide, effect is more excellent；Work as ethers
Solvent is ethyl methyl ether, and esters solvent is ethylene carbonate, dimethyl carbonate；Dystectic ethylene carbonate is mixed with low melting point solvent
Its application performance is effectively improved after conjunction；Especially on the basis of ethylene carbonate, dimethyl carbonate, ethyl methyl ether is added, finally
The discharge performance of electrolyte significantly improves.
Preferably, the volume ratio of the ether solvent and the esters solvent is：8~12:1；
It is highly preferred that the organic solvent is：Volume ratio 5:5:1 ethylene carbonate, dimethyl carbonate, ethyl methyl ether.
Wherein, when the organic solvent is prepared in the following way, the electrolyte that is effectively definitely configured
Quality.
The preparation of the organic solvent is specially：In the environment of dew point is less than 3ppm less than -45 DEG C, oxygen content, by institute
It states ether solvent and the esters solvent is sufficiently mixed in proportion.
Wherein, the lithium salts is selected from lithium iodide, lithium perchlorate, LiBF4, hexafluoroarsenate lithium, lithium hexafluoro phosphate, three
One or more of methyl fluoride Sulfonic Lithium；
Preferably, the lithium salts of 0.8-1.5mol is dissolved in organic solvent described in every 1L；
It is highly preferred that dissolving the lithium salts of 1mol in organic solvent described in per 1L.
Preferably, three (trimethyl silane) borate and 3,3', the water content of 5,5'- tetramethyl benzidines is not higher than
5ppm。
It is a further object of the present invention to provide the preparation methods of above-mentioned electrolyte, specially：In 0-10 DEG C of temperature
Under, lithium salts is added in organic solvent, after so that it is fully dissolved, adds three (trimethyl silane) borates and 3,3', 5,5'-
Tetramethyl benzidine is to get the ternary battery electrolytic solution.
The present invention provides a kind of preferred embodiment, and the preparation method is specifically, at a temperature of 0-10 DEG C, by hexafluorophosphoric acid
Lithium is added by the concentration of 1mol/L in organic solvent of the water content not higher than 10ppm, after so that it is fully dissolved, is added described in accounting for
Three (trimethyl silane) borates of electrolyte total weight 4% and 4% 3,3', 5,5'- tetramethyl benzidines, are sufficiently mixed
Afterwards to get the ternary battery electrolytic solution；
Wherein, three (trimethyl silane) borate and 3,3', the water content of 5,5'- tetramethyl benzidines is not higher than
5ppm。
Any of the above-described preparation method is made electrolyte and can be used for ternary battery.
Ternary battery of the present invention passes through three (trimethyl silane) borates and 3,3', 5,5'- tetramethyl benzidines
Immixture, can effectively avoid ternary dynamic lithium battery voltage occur in high-multiplying power discharge and decline that fast, discharge capacity is insufficient
The phenomenon that, to solve the problems, such as to perplex the ternary battery high-multiplying power discharge off-capacity of industry all the time.
Specific implementation mode
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment 1
The present embodiment provides a kind of preparation methods of ternary battery electrolytic solution；Include the following steps：
1) it is less than -45 DEG C in dew point, oxygen content is less than in the environment of 3ppm, is 5 by volume ratio:5:1 ethylene carbonate,
Dimethyl carbonate, ethyl methyl ether are sufficiently mixed, and it is spare to be configured to organic solvent；
2) at a temperature of 0-10 DEG C, water content is added not higher than 10ppm's by the concentration of 1mol/L in lithium hexafluoro phosphate
In organic solvent, after so that it is fully dissolved, add account for the electrolyte total weight 4% three (trimethyl silane) borates and
The 3,3' of 4%, 5,5'- tetramethyl benzidines, to get the ternary battery electrolytic solution after being sufficiently mixed；
Wherein, three (trimethyl silane) borate and 3,3', the water content of 5,5'- tetramethyl benzidines is not higher than
5ppm；
Embodiment 2
The present embodiment provides a kind of preparation method of ternary battery electrolytic solution, the difference of the present embodiment and embodiment 1 is only
It is：
In step 2) " addition accounts for three (trimethyl silane) borates of the electrolyte total weight 4% and 4% 3,3',
5,5'- tetramethyl benzidines " replace with that " addition accounts for three (trimethyl silane) borates and 2% of the electrolyte total weight 2%
3,3', 5,5'- tetramethyl benzidines ".
Embodiment 3
The present embodiment provides a kind of preparation method of ternary battery electrolytic solution, the difference of the present embodiment and embodiment 1 is only
It is：
In step 2) " addition accounts for three (trimethyl silane) borates of the electrolyte total weight 4% and 4% 3,3',
5,5'- tetramethyl benzidines " replace with " three (trimethyl silane) borates that addition accounts for the electrolyte total weight 2% ".
Embodiment 4
The present embodiment provides a kind of preparation method of ternary battery electrolytic solution, the difference of the present embodiment and embodiment 1 is only
It is：
In step 2) " addition accounts for three (trimethyl silane) borates of the electrolyte total weight 4% and 4% 3,3',
5,5'- tetramethyl benzidines " replace with " addition accounts for the 3,3' of the electrolyte total weight 2%, 5,5'- tetramethyl benzidines ".
Embodiment 5
The present embodiment provides a kind of preparation methods of ternary battery electrolytic solution；The difference of the present embodiment and embodiment 1 is only
It is：
Ethylene carbonate in step 1), dimethyl carbonate, ethyl methyl ether volume ratio be 1:1:1.
Embodiment 6
The present embodiment provides a kind of preparation methods of ternary battery electrolytic solution；The difference of the present embodiment and embodiment 1 is only
It is：
Ethylene carbonate in step 1), dimethyl carbonate, ethyl methyl ether volume ratio be 1:4:4.
Embodiment 7
The present embodiment provides a kind of preparation methods of ternary battery electrolytic solution；The difference of the present embodiment and embodiment 1 is only
It is：
" ethyl methyl ether " replaces with " glycol dimethyl ether " in step 1).
Comparative example 1
The present embodiment provides a kind of preparation methods of ternary battery electrolytic solution；The difference of this comparative example and embodiment 1 is only
It is：
To " be 5 by volume ratio in step 1):5:1 ethylene carbonate, dimethyl carbonate, ethyl methyl ether are sufficiently mixed " it replaces
" to be 1 by volume ratio:1 ethylene carbonate, dimethyl carbonate are sufficiently mixed ".
Experimental example 1
186590 rectangular aluminum-shell batteries and commercially available are made in electrolyte obtained by Examples 1 to 7, comparative example 1
18650 batteries,《GB-T 31484-2015 power accumulator cycle lives for electric vehicle require and test method》Condition
Under, 1C, 3C discharge capacity are detected, it is as a result as follows：
Table 1
Although above having used general explanation, specific implementation mode and experiment, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (10)
1. a kind of electrolyte of ternary battery, which is characterized in that be formulated by lithium salts, organic solvent, functional additive；
Wherein, the functional additive is three (trimethyl silane) borates and 3,3', 5,5'- tetramethyl benzidines.
2. electrolyte according to claim 1, which is characterized in that three (trimethyl silane) borate and 3,3', 5,
The sum of the weight of 5'- tetramethyl benzidines accounts for the 1%~10% of the electrolyte weight；Preferably 4%~8%；
It is highly preferred that three (trimethyl silane) borate and 3,3', the water content of 5,5'- tetramethyl benzidines is not higher than
5ppm。
3. electrolyte according to claim 1 or 2, which is characterized in that three (trimethyl silane) borate with it is described
The weight ratio of 3,3', 5,5'- tetramethyl benzidine is 0.5~2:1；Preferably 1:1.
4. electrolyte according to claim 3, which is characterized in that the organic solvent is that ether solvent and/or esters are molten
Agent；
Preferably, the ether solvent is selected from ether, ethyl methyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diformazan
It is one or more in ether, tetraethyleneglycol dimethyl ether, ethylene glycol monoemethyl ether, dioxolane, dioxane；
The esters solvent is selected from propene carbonate, ethylene carbonate, butylene, dimethyl carbonate, diethyl carbonate, carbon
Sour first butyl ester, ethyl butyl carbonate, dibutyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, chloroethylenes carbonic acid
It is one or more in ester, ethyl acetate, propyl acetate, ethyl propionate, methyl butyrate；
It is highly preferred that the water content of the organic solvent is not higher than 10ppm.
5. according to Claims 1 to 4 any one of them electrolyte, which is characterized in that the organic solvent be ether solvent and
The mixed solvent of esters solvent；
Preferably, the volume ratio of the ether solvent and the esters solvent is：8~12:1；
It is highly preferred that the organic solvent is：Volume ratio 5:5:1 ethylene carbonate, dimethyl carbonate, ethyl methyl ether.
6. according to Claims 1 to 5 any one of them electrolyte, which is characterized in that the preparation of the organic solvent is specially：
It is in the environment of dew point is less than 3ppm less than -45 DEG C, oxygen content, the ether solvent and the esters solvent is abundant in proportion
Mixing.
7. according to claim 1~6 any one of them electrolyte, which is characterized in that the lithium salts is selected from lithium iodide, perchloric acid
One or more of lithium, LiBF4, hexafluoroarsenate lithium, lithium hexafluoro phosphate, trifluoromethyl sulfonic acid lithium；
Preferably, the lithium salts of 0.8-1.5mol is dissolved in organic solvent described in every 1L；
It is highly preferred that dissolving the lithium salts of 1mol in organic solvent described in per 1L.
8. the preparation method of any one of claim 1~7 electrolyte lithium salts is added organic at a temperature of 0-10 DEG C
In solvent, after so that it is fully dissolved, add three (trimethyl silane) borates and 3,3', 5,5'- tetramethyl benzidines to get
The ternary battery electrolytic solution.
9. preparation method according to claim 8, which is characterized in that at a temperature of 0-10 DEG C, lithium hexafluoro phosphate is pressed
The concentration of 1mol/L is added in organic solvent of the water content not higher than 10ppm, after so that it is fully dissolved, adds and accounts for the electrolysis
Three (trimethyl silane) borates of liquid total weight 4% and 4% 3,3', 5,5'- tetramethyl benzidines, after being sufficiently mixed, i.e.,
Obtain the ternary battery electrolytic solution；
Wherein, the water content of three (trimethyl silane) borate and 3,3', 5,5'- tetramethyl benzidines is not higher than 5ppm.
10. a kind of ternary battery, which is characterized in that including the electrolyte described in claim 9.
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| CN201810101966.2A CN108417892B (en) | 2018-02-01 | 2018-02-01 | Electrolyte for ternary battery and preparation method thereof |
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| CN201810101966.2A CN108417892B (en) | 2018-02-01 | 2018-02-01 | Electrolyte for ternary battery and preparation method thereof |
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| CN108417892B CN108417892B (en) | 2020-07-07 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113725488A (en) * | 2021-08-30 | 2021-11-30 | 中汽创智科技有限公司 | Metal battery electrolyte and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5837112A (en) * | 1997-02-28 | 1998-11-17 | Dragerwerk Ag | Electrochemical measuring cell for detecting phosgene |
| CN105789686A (en) * | 2016-03-18 | 2016-07-20 | 东莞市凯欣电池材料有限公司 | High-capacity lithium ion battery electrolyte and high-capacity lithium ion battery |
| CN106611869A (en) * | 2015-10-26 | 2017-05-03 | 三星Sdi株式会社 | Rechargeable lithium battery |
-
2018
- 2018-02-01 CN CN201810101966.2A patent/CN108417892B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5837112A (en) * | 1997-02-28 | 1998-11-17 | Dragerwerk Ag | Electrochemical measuring cell for detecting phosgene |
| CN106611869A (en) * | 2015-10-26 | 2017-05-03 | 三星Sdi株式会社 | Rechargeable lithium battery |
| CN105789686A (en) * | 2016-03-18 | 2016-07-20 | 东莞市凯欣电池材料有限公司 | High-capacity lithium ion battery electrolyte and high-capacity lithium ion battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113725488A (en) * | 2021-08-30 | 2021-11-30 | 中汽创智科技有限公司 | Metal battery electrolyte and application thereof |
| CN113725488B (en) * | 2021-08-30 | 2023-07-25 | 中汽创智科技有限公司 | Electrolyte for metal battery and application thereof |
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| CN108417892B (en) | 2020-07-07 |
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