CN106099193A - A kind of low temperature electrolyte for lithium ion battery - Google Patents
A kind of low temperature electrolyte for lithium ion battery Download PDFInfo
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- CN106099193A CN106099193A CN201610613779.3A CN201610613779A CN106099193A CN 106099193 A CN106099193 A CN 106099193A CN 201610613779 A CN201610613779 A CN 201610613779A CN 106099193 A CN106099193 A CN 106099193A
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- organic solvent
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- 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
- 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
- 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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- 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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Abstract
The present invention relates to a kind of low temperature electrolyte for lithium ion battery, its preparation method comprise the steps: (1) at dew point less than 40 DEG C, oxygen content less than in the environment of 2ppm, following materials is configured as organic solvent according to equal in quality ratio；(2) moisture of above-mentioned organic solvent is reduced to below 8ppm；(3) addition occupies the following materials of machine solvent weight percent 5%～10% in organic solvent；(4) mixture in step (3) adds the following materials occupying machine solvent weight percent 5%～8%；(5), after the solvent temperature obtained in step (4) is down to 0～2 DEG C, in nonaqueous electrolytic solution, adds the following lithium salts occupying machine solvent weight percent 40%～60% under stirring, after mix homogeneously, obtain this product.The process of the inventive method preparation electrolyte is simple, easy to operate, it is adaptable to commercial production.
Description
Technical field
The present invention relates to a kind of low temperature electrolyte for lithium ion battery, belong to technical field of lithium ion.
Background technology
Electrolyte is the important component part of lithium battery, and it is the ion playing conduction between battery positive and negative electrode
Conductor, the performance of itself and the state of interface formed with both positive and negative polarity thereof largely affect the performance of battery.Excellent lithium
Battery nonaqueous electrolytic solution should possess some requirement following: (1) chemical stability is good, with the both positive and negative polarity active substance in battery and collection
There is not chemical reaction in fluid (general aluminium foil and Copper Foil)；(2) electrochemical stability window width；(3) ionic conductivity is high, electronics
Electrical conductivity is low；(4) temperature range is properly that boiling point is high, and fusing point is low；(5) safety and low toxicity, non-environmental-pollution.
Lithium battery is the easily viscosity increase when transport and storage with nonaqueous electrolytic solution, and produces battery along with when storing
Between prolongation, internal resistance the most constantly increases, especially when dioxolanes ratio is higher, electrolyte viscosity B coefficent and in battery
Resistance impact aggravation.The main cause causing this phenomenon is in storage and transport process, and dioxolanes equal solvent is slowly polymerized, and acyclic acidic
The existence of border, hot environment and metal cation can accelerate polyreaction.The most any its viscosity of stablizing is that individual needs solves
Problem.
Summary of the invention
It is an object of the invention to provide a kind of low temperature electrolyte for lithium ion battery, stable viscosity can be prepared and reduce lithium
The electrolyte of the internal resistance of cell, in order to use the most as required.
To achieve these goals, technical scheme is as follows.
A kind of low temperature electrolyte for lithium ion battery, its preparation method comprises the steps:
(1) at dew point less than-40 DEG C, oxygen content less than in the environment of 2ppm, following materials is joined according to equal in quality ratio
Be set to as organic solvent: dimethyl carbonate, fluorinated ethylene carbonate, vinylene carbonate, dimethyl sulfoxide, polyvinyl alcohol, 1,
3-propane sultone, tricresyl phosphate chloro Arrcostab, Ethyl methyl carbonate；
(2) moisture of above-mentioned organic solvent is reduced to below 8ppm；
(3) add in organic solvent and occupy the following materials of machine solvent weight percent 5%～10%: cadmium sulfate, two
Isopropyl carbimide, its mass ratio is 3～5:1；
(4) mixture in step (3) adds and occupies the following materials of machine solvent weight percent 5%～8%: 2-mercapto
Base benzimidazole allyl sulphide, methyl a pair of horses going side by side triazole, 3-(1,3-bis-chloro isopropyl) phosphate ester, its mass ratio be 2～4:3～
5:1；
(5), after the solvent temperature obtained in step (4) is down to 0～2 DEG C, adds in nonaqueous electrolytic solution under stirring and account for
The following lithium salts of organic solvent percentage by weight 40%～60%: double oxalic acid borate lithiums, cobalt acid lithium, thiocyanation lithium, its quality
Ratio is 2～4:3～5:1, obtains this product after mix homogeneously.
Further, in step (5), controlling described temperature in adition process is 5 DEG C～10 DEG C.
This beneficial effect of the invention is: the viscosity in the case of storing 60 days of the electrolyte in the present invention does not occurs
Change, effectively reduces the internal resistance after battery storage, and controls to add in nonaqueous electrolytic solution under specified temp lithium after injecting battery
Salt, the most effectively stops electrolyte polyreaction after producing, transporting and inject battery, the process of the method preparation electrolyte
Simply, easy to operate, it is adaptable to commercial production.
Detailed description of the invention
Below in conjunction with embodiment, the detailed description of the invention of the present invention is described, in order to be better understood from the present invention.
Embodiment 1
Low temperature electrolyte for lithium ion battery in the present embodiment, its preparation method comprises the steps:
(1) at dew point less than-40 DEG C, oxygen content less than in the environment of 2ppm, following materials is joined according to equal in quality ratio
Be set to as organic solvent: dimethyl carbonate, fluorinated ethylene carbonate, vinylene carbonate, dimethyl sulfoxide, polyvinyl alcohol, 1,
3-propane sultone, tricresyl phosphate chloro Arrcostab, Ethyl methyl carbonate；
(2) moisture of above-mentioned organic solvent is reduced to below 8ppm；
(3) add in organic solvent and occupy the following materials of machine solvent weight percent 5%: cadmium sulfate, diisopropyl
Carbimide, its mass ratio is 3:1；
(4) mixture in step (3) adds and occupies the following materials of machine solvent weight percent 8%: 2-sulfydryl benzene
And imidazoles allyl sulphide, methyl a pair of horses going side by side triazole, 3-(1,3-bis-chloro isopropyl) phosphate ester, its mass ratio is 2:3:1；
(5), after the solvent temperature obtained in step (4) is down to 0～2 DEG C, adds in nonaqueous electrolytic solution under stirring and account for
The following lithium salts of organic solvent percentage by weight 40%: double oxalic acid borate lithiums, cobalt acid lithium, thiocyanation lithium, its mass ratio is 2:
3:1, obtains this product after mix homogeneously.
In step (5), controlling described temperature in adition process is 5 DEG C.
Performance test data is as follows:
Electrolyte stores experiment
| Viscosity before storing | Viscosity after storing 30 days | Viscosity after storing 60 days |
| 1.18mPa·S | 1.19mPa·S | 1.19mPa·S |
Inject internal resistance of cell change after lithium-ferrous disulfide AA battery
| Internal resistance before storing | Internal resistance after storing 30 days | Internal resistance after storing 60 days |
| 182mΩ | 185mΩ | 189mΩ |
Embodiment 2
Low temperature electrolyte for lithium ion battery in the present embodiment, its preparation method comprises the steps:
(1) at dew point less than-40 DEG C, oxygen content less than in the environment of 2ppm, following materials is joined according to equal in quality ratio
Be set to as organic solvent: dimethyl carbonate, fluorinated ethylene carbonate, vinylene carbonate, dimethyl sulfoxide, polyvinyl alcohol, 1,
3-propane sultone, tricresyl phosphate chloro Arrcostab, Ethyl methyl carbonate；
(2) moisture of above-mentioned organic solvent is reduced to below 8ppm；
(3) add in organic solvent and occupy the following materials of machine solvent weight percent 10%: cadmium sulfate, diisopropyl
Carbimide, its mass ratio is 5:1；
(4) mixture in step (3) adds and occupies the following materials of machine solvent weight percent 5%: 2-sulfydryl benzene
And imidazoles allyl sulphide, methyl a pair of horses going side by side triazole, 3-(1,3-bis-chloro isopropyl) phosphate ester, its mass ratio is 4:5:1；
(5), after the solvent temperature obtained in step (4) is down to 0～2 DEG C, adds in nonaqueous electrolytic solution under stirring and account for
The following lithium salts of organic solvent percentage by weight 60%: double oxalic acid borate lithiums, cobalt acid lithium, thiocyanation lithium, its mass ratio is 4:
5:1, obtains this product after mix homogeneously.
In step (5), controlling described temperature in adition process is 10 DEG C.
Performance test data is as follows:
Electrolyte stores experiment
| Viscosity before storing | Viscosity after storing 30 days | Viscosity after storing 60 days |
| 1.23mPa·S | 1.23mPa·S | 1.27mPa·S |
Inject internal resistance of cell change after lithium-ferrous disulfide AA battery
| Internal resistance before storing | Internal resistance after storing 30 days | Internal resistance after storing 60 days |
| 192mΩ | 194mΩ | 196mΩ |
Embodiment 3
Low temperature electrolyte for lithium ion battery in the present embodiment, its preparation method comprises the steps:
(1) at dew point less than-40 DEG C, oxygen content less than in the environment of 2ppm, following materials is joined according to equal in quality ratio
Be set to as organic solvent: dimethyl carbonate, fluorinated ethylene carbonate, vinylene carbonate, dimethyl sulfoxide, polyvinyl alcohol, 1,
3-propane sultone, tricresyl phosphate chloro Arrcostab, Ethyl methyl carbonate；
(2) moisture of above-mentioned organic solvent is reduced to below 8ppm；
(3) add in organic solvent and occupy the following materials of machine solvent weight percent 8%: cadmium sulfate, diisopropyl
Carbimide, its mass ratio is 4:1；
(4) mixture in step (3) adds and occupies the following materials of machine solvent weight percent 6%: 2-sulfydryl benzene
And imidazoles allyl sulphide, methyl a pair of horses going side by side triazole, 3-(1,3-bis-chloro isopropyl) phosphate ester, its mass ratio is 3:4:1；
(5), after the solvent temperature obtained in step (4) is down to 0～2 DEG C, adds in nonaqueous electrolytic solution under stirring and account for
The following lithium salts of organic solvent percentage by weight 50%: double oxalic acid borate lithiums, cobalt acid lithium, thiocyanation lithium, its mass ratio is 3:
4:1, obtains this product after mix homogeneously.
In step (5), controlling described temperature in adition process is 8 DEG C.
Performance test data is as follows:
Electrolyte stores experiment
| Viscosity before storing | Viscosity after storing 30 days | Viscosity after storing 60 days |
| 1.38mPa·S | 1.38mPa·S | 1.41mPa·S |
Inject internal resistance of cell change after lithium-ferrous disulfide AA battery
| Internal resistance before storing | Internal resistance after storing 30 days | Internal resistance after storing 60 days |
| 179mΩ | 180mΩ | 181mΩ |
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (2)
1. a low temperature electrolyte for lithium ion battery, it is characterised in that: its preparation method comprises the steps:
(1) at dew point less than-40 DEG C, oxygen content less than in the environment of 2ppm, following materials is configured to according to equal in quality ratio
For organic solvent: dimethyl carbonate, fluorinated ethylene carbonate, vinylene carbonate, dimethyl sulfoxide, polyvinyl alcohol, 1,3-third
Sultone, tricresyl phosphate chloro Arrcostab, Ethyl methyl carbonate；
(2) moisture of above-mentioned organic solvent is reduced to below 8ppm；
(3) add in organic solvent and occupy the following materials of machine solvent weight percent 5%～10%: cadmium sulfate, diisopropyl
Base carbimide, its mass ratio is 3～5:1；
(4) mixture in step (3) adds and occupies the following materials of machine solvent weight percent 5%～8%: 2-sulfydryl benzene
And imidazoles allyl sulphide, methyl a pair of horses going side by side triazole, 3-(1,3-bis-chloro isopropyl) phosphate ester, its mass ratio is 2～4:3～5:1；
(5), after the solvent temperature obtained in step (4) is down to 0～2 DEG C, adds in nonaqueous electrolytic solution under stirring and occupy machine
The following lithium salts of solvent weight percent 40%～60%: double oxalic acid borate lithiums, cobalt acid lithium, thiocyanation lithium, its mass ratio is 2
～4:3～5:1, obtain this product after mix homogeneously.
Low temperature electrolyte for lithium ion battery preparation method the most according to claim 1, it is characterised in that: described step
(5), in, controlling described temperature in adition process is 5 DEG C～10 DEG C.
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| CN201610613779.3A CN106099193B (en) | 2016-07-29 | 2016-07-29 | A kind of low temperature electrolyte for lithium ion battery |
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| CN201610613779.3A CN106099193B (en) | 2016-07-29 | 2016-07-29 | A kind of low temperature electrolyte for lithium ion battery |
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| CN106099193A true CN106099193A (en) | 2016-11-09 |
| CN106099193B CN106099193B (en) | 2019-01-25 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024007318A1 (en) * | 2022-07-08 | 2024-01-11 | 宁德时代新能源科技股份有限公司 | Electrolyte solution and lithium-ion battery comprising same |
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| CN102361097A (en) * | 2011-11-14 | 2012-02-22 | 中国海洋石油总公司 | Preparation method of low-temperature electrolyte for lithium iron phosphate power battery |
| CN103219544A (en) * | 2013-04-10 | 2013-07-24 | 山东威高东生新能源科技有限公司 | Low-temperature electrolyte for ternary power lithium ion battery and preparation method |
| CN103378360A (en) * | 2012-04-24 | 2013-10-30 | 张家港市国泰华荣化工新材料有限公司 | Organic electrolyte capable of improving low-temperature performance of lithium manganese battery |
| CN103762383A (en) * | 2014-01-14 | 2014-04-30 | 南昌大学 | Lithium ion battery low-temperature electrolyte and preparation method thereof |
| CN105047996A (en) * | 2015-05-28 | 2015-11-11 | 河南省法恩莱特新能源科技有限公司 | Lithium ion battery low temperature electrolyte and lithium ion battery |
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2016
- 2016-07-29 CN CN201610613779.3A patent/CN106099193B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102361097A (en) * | 2011-11-14 | 2012-02-22 | 中国海洋石油总公司 | Preparation method of low-temperature electrolyte for lithium iron phosphate power battery |
| CN103378360A (en) * | 2012-04-24 | 2013-10-30 | 张家港市国泰华荣化工新材料有限公司 | Organic electrolyte capable of improving low-temperature performance of lithium manganese battery |
| CN103219544A (en) * | 2013-04-10 | 2013-07-24 | 山东威高东生新能源科技有限公司 | Low-temperature electrolyte for ternary power lithium ion battery and preparation method |
| CN103762383A (en) * | 2014-01-14 | 2014-04-30 | 南昌大学 | Lithium ion battery low-temperature electrolyte and preparation method thereof |
| CN105047996A (en) * | 2015-05-28 | 2015-11-11 | 河南省法恩莱特新能源科技有限公司 | Lithium ion battery low temperature electrolyte and lithium ion battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024007318A1 (en) * | 2022-07-08 | 2024-01-11 | 宁德时代新能源科技股份有限公司 | Electrolyte solution and lithium-ion battery comprising same |
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| CN106099193B (en) | 2019-01-25 |
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Granted publication date: 20190125 Termination date: 20200729 |