CN106025362B - A kind of electrolyte of low temp lithium ion battery - Google Patents

A kind of electrolyte of low temp lithium ion battery Download PDF

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Publication number
CN106025362B
CN106025362B CN201610488970.XA CN201610488970A CN106025362B CN 106025362 B CN106025362 B CN 106025362B CN 201610488970 A CN201610488970 A CN 201610488970A CN 106025362 B CN106025362 B CN 106025362B
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solvent
electrolyte
weight percent
organic solvent
lithium
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CN106025362A (en
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郑君臣
黄国圈
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Yinke Tianrun New Energy Materials (Shandong) Co.,Ltd.
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Huaying City High-Tech Dragon Electronic Science And Technology Co Ltd
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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
    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention relates to a kind of electrolyte of low temp lithium ion battery, preparation method includes the following steps: that following materials in the environment of dew point is less than 2ppm lower than -40 DEG C, oxygen content, are configured as organic solvent according to identical mass ratio by (1)；(2) moisture of above-mentioned organic solvent is reduced to 8ppm or less；(3) following materials for occupying solvent weight percent 5%~10% are added in organic solvent；(4) following materials for occupying solvent weight percent 5%~8% are added in the mixture in step (3)；(5) after the solvent temperature that step (4) obtain is down to 0~2 DEG C, the following lithium salts for occupying solvent weight percent 40%~60% is added under stirring into nonaqueous electrolytic solution, obtains this product after mixing.The process that the method for the present invention prepares electrolyte is simple, easy to operate, is suitable for industrial production.

Description

A kind of electrolyte of low temp lithium ion battery
Technical field
The present invention relates to a kind of electrolyte of low temp lithium ion battery, belong to technical field of lithium ion.
Background technique
Electrolyte is the important component of lithium battery, it is the ion that conduction is played between battery positive and negative electrode Conductor, the performance of itself and its state of interface formed with positive and negative anodes largely influence the performance of battery.Excellent lithium Battery nonaqueous electrolytic solution should have following requirement: (1) chemical stability is good, with the positive and negative anodes active material sum aggregate in battery Fluid (general aluminium foil and copper foil) does not chemically react；(2) electrochemical stability window is wide；(3) ionic conductivity is high, electronics 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.
Summary of the invention
The purpose of the present invention is to provide a kind of electrolyte of low temp lithium ion battery, can prepare stable viscosity and reduce lithium The electrolyte of the internal resistance of cell, preferably to use as needed.
To achieve the goals above, technical scheme is as follows.
A kind of electrolyte of low temp lithium ion battery, preparation method include the following steps:
(1) in the environment of dew point is less than 2ppm lower than -40 DEG C, oxygen content, following materials are matched according to identical mass ratio It is set to as organic solvent: stannous fluoboric acid, butyl methyl tetrafluoroborate, dimethyl carbonate, diethyl carbonate, hydrogen sulfate Salt, vinylene carbonate, cetyl trimethylammonium bromide, tetraethyleneglycol dimethyl ether；
(2) moisture of above-mentioned organic solvent is reduced to 8ppm or less；
(3) following materials for occupying solvent weight percent 5%~10%: 2,6- bis- tertiary fourths are added in organic solvent Base paracresol, poly-aspartic-acid, mass ratio are 3~5:1；
(4) following materials for occupying solvent weight percent 5%~8%: carbonic acid are added in the mixture in step (3) Vinylene, tetraethyl ammonium tetrafluoroborate, diphenyl sulfoxide, mass ratio are 2~4:3~5:1；
(5) it after the solvent temperature that step (4) obtain is down to 0~2 DEG C, is added and accounts for into nonaqueous electrolytic solution under stirring The following lithium salts of organic solvent weight percent 40%~60%: trifluoromethyl sulfonic acid lithium, bis trifluoromethyl sulfimide lithium, double Ethanedioic acid Lithium bis (oxalate) borate, mass ratio are 2~4:3~5:1, obtain this product after mixing.
Further, in step (5), it is 5 DEG C~10 DEG C that the temperature is controlled in adition process.
Invention has the beneficial effects that: the present invention in electrolyte store 60 days in the case where viscosity do not occur substantially The internal resistance after battery storage is effectively reduced after injecting battery in variation；And it controls and lithium is added under specific temperature into nonaqueous electrolytic solution Salt, also effectively prevents polymerization reaction of the electrolyte after production, transport and injection battery, and this method prepares the process of electrolyte Simply, easy to operate, it is suitable for industrial production.
Specific embodiment
A specific embodiment of the invention is described below with reference to embodiment, to better understand the present invention.
Embodiment 1
Electrolyte of low temp lithium ion battery in the present embodiment, preparation method include the following steps:
(1) in the environment of dew point is less than 2ppm lower than -40 DEG C, oxygen content, following materials are matched according to identical mass ratio It is set to as organic solvent: stannous fluoboric acid, butyl methyl tetrafluoroborate, dimethyl carbonate, diethyl carbonate, hydrogen sulfate Salt, vinylene carbonate, cetyl trimethylammonium bromide, tetraethyleneglycol dimethyl ether；
(2) moisture of above-mentioned organic solvent is reduced to 8ppm or less；
(3) following materials for occupying solvent weight percent 5% are added in organic solvent: 2,6- di-t-butyls are to first Phenol, poly-aspartic-acid, mass ratio 3:1；
(4) following materials for occupying solvent weight percent 8%: carbonic acid Asia second are added in the mixture in step (3) Enester, tetraethyl ammonium tetrafluoroborate, diphenyl sulfoxide, mass ratio 2:3:1；
(5) it after the solvent temperature that step (4) obtain is down to 0~2 DEG C, is added and accounts for into nonaqueous electrolytic solution under stirring The following lithium salts of organic solvent weight percent 40%: trifluoromethyl sulfonic acid lithium, bis trifluoromethyl sulfimide lithium, double ethanedioic acids Lithium bis (oxalate) borate, mass ratio 2:3:1, obtains this product after mixing.
In step (5), it is 5 DEG C that the temperature is controlled in adition process.
Performance test data is as follows:
Electrolyte storage experiment
Viscosity before storing Viscosity after storage 30 days Viscosity after storage 60 days
1.18mPa·S 1.18mPa·S 1.19mPa·S
The internal resistance of cell changes after injecting lithium-ferrous disulfide AA battery
Internal resistance before storing Internal resistance after storage 30 days Internal resistance after storage 60 days
182mΩ 186mΩ 189mΩ
Embodiment 2
Electrolyte of low temp lithium ion battery in the present embodiment, preparation method include the following steps:
(1) in the environment of dew point is less than 2ppm lower than -40 DEG C, oxygen content, following materials are matched according to identical mass ratio It is set to as organic solvent: stannous fluoboric acid, butyl methyl tetrafluoroborate, dimethyl carbonate, diethyl carbonate, hydrogen sulfate Salt, vinylene carbonate, cetyl trimethylammonium bromide, tetraethyleneglycol dimethyl ether；
(2) moisture of above-mentioned organic solvent is reduced to 8ppm or less；
(3) following materials for occupying solvent weight percent 10%: 2,6- di-t-butyls pair are added in organic solvent Cresols, poly-aspartic-acid, mass ratio 5:1；
(4) following materials for occupying solvent weight percent 5%: carbonic acid Asia second are added in the mixture in step (3) Enester, tetraethyl ammonium tetrafluoroborate, diphenyl sulfoxide, mass ratio 4:5:1；
(5) it after the solvent temperature that step (4) obtain is down to 0~2 DEG C, is added and accounts for into nonaqueous electrolytic solution under stirring The following lithium salts of organic solvent weight percent 60%: trifluoromethyl sulfonic acid lithium, bis trifluoromethyl sulfimide lithium, double ethanedioic acids Lithium bis (oxalate) borate, mass ratio 4:5:1, obtains this product after mixing.
In step (5), it is 10 DEG C that the temperature is controlled in adition process.
Performance test data is as follows:
Electrolyte storage experiment
Viscosity before storing Viscosity after storage 30 days Viscosity after storage 60 days
1.23mPa·S 1.23mPa·S 1.27mPa·S
The internal resistance of cell changes after injecting lithium-ferrous disulfide AA battery
Internal resistance before storing Internal resistance after storage 30 days Internal resistance after storage 60 days
192mΩ 194mΩ 197mΩ
Embodiment 3
Electrolyte of low temp lithium ion battery in the present embodiment, preparation method include the following steps:
(1) in the environment of dew point is less than 2ppm lower than -40 DEG C, oxygen content, following materials are matched according to identical mass ratio It is set to as organic solvent: stannous fluoboric acid, butyl methyl tetrafluoroborate, dimethyl carbonate, diethyl carbonate, hydrogen sulfate Salt, vinylene carbonate, cetyl trimethylammonium bromide, tetraethyleneglycol dimethyl ether；
(2) moisture of above-mentioned organic solvent is reduced to 8ppm or less；
(3) following materials for occupying solvent weight percent 8% are added in organic solvent: 2,6- di-t-butyls are to first Phenol, poly-aspartic-acid, mass ratio 4:1；
(4) following materials for occupying solvent weight percent 6%: carbonic acid Asia second are added in the mixture in step (3) Enester, tetraethyl ammonium tetrafluoroborate, diphenyl sulfoxide, mass ratio 3:4:1；
(5) it after the solvent temperature that step (4) obtain is down to 0~2 DEG C, is added and accounts for into nonaqueous electrolytic solution under stirring The following lithium salts of organic solvent weight percent 50%: trifluoromethyl sulfonic acid lithium, bis trifluoromethyl sulfimide lithium, double ethanedioic acids Lithium bis (oxalate) borate, mass ratio 3:4:1, obtains this product after mixing.
In step (5), it is 8 DEG C that the temperature is controlled in adition process.
Performance test data is as follows:
Electrolyte storage experiment
Viscosity before storing Viscosity after storage 30 days Viscosity after storage 60 days
1.38mPa·S 1.38mPa·S 1.41mPa·S
The internal resistance of cell changes after injecting lithium-ferrous disulfide AA battery
Internal resistance before storing Internal resistance after storage 30 days Internal resistance after storage 60 days
177mΩ 179mΩ 181mΩ
The above is a preferred embodiment of the present invention, it is noted that for those skilled in the art For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as Protection scope of the present invention.

Claims (2)

1. a kind of electrolyte of low temp lithium ion battery, it is characterised in that: preparation method includes the following steps:
(1) in the environment of dew point is less than 2ppm lower than -40 DEG C, oxygen content, following materials are configured to according to identical mass ratio For organic solvent: stannous fluoboric acid, butyl methyl tetrafluoroborate, dimethyl carbonate, diethyl carbonate, disulfate, Vinylene carbonate, cetyl trimethylammonium bromide, tetraethyleneglycol dimethyl ether；
(2) moisture of above-mentioned organic solvent is reduced to 8ppm or less；
(3) following materials for occupying solvent weight percent 5%~10%: 2,6- di-t-butyls pair are added in organic solvent Cresols, poly-aspartic-acid, mass ratio are 3~5:1；
(4) following materials for occupying solvent weight percent 5%~8%: carbonic acid Asia second are added in the mixture in step (3) Enester, tetraethyl ammonium tetrafluoroborate, diphenyl sulfoxide, mass ratio are 2~4:3~5:1；
(5) after the solvent temperature that step (4) obtain is down to 0~2 DEG C, add under stirring into the solvent of step (4) acquisition Enter to occupy the following lithium salts of solvent weight percent 40%~60%: trifluoromethyl sulfonic acid lithium, bis trifluoromethyl sulfimide Lithium, double ethanedioic acid Lithium bis (oxalate) borates, mass ratio are 2~4:3~5:1, obtain this product after mixing.
2. electrolyte of low temp lithium ion battery according to claim 1, it is characterised in that: in the step (5), be added In the process controlled at 5 DEG C~10 DEG C.
CN201610488970.XA 2016-06-28 2016-06-28 A kind of electrolyte of low temp lithium ion battery Active CN106025362B (en)

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CN107946646A (en) * 2017-04-14 2018-04-20 云南锡业集团（控股）有限责任公司 A kind of square low-temperature lithium ion battery and preparation method thereof
CN107195971A (en) * 2017-04-28 2017-09-22 山东海容电源材料股份有限公司 A kind of low form lithium battery electrolytes and preparation method thereof
CN107527750A (en) * 2017-08-23 2017-12-29 吴江佳亿电子科技有限公司 A kind of electrolytic solution for super capacitor of low form, its preparation method and ultracapacitor
CN110875495B (en) * 2018-08-29 2021-08-13 中南大学 Electrolyte for improving cycle performance of lithium-sulfur battery and preparation thereof
CN110994031B (en) * 2019-12-19 2021-11-30 湖南美尼科技有限公司 Fast-charging high-temperature-resistant electrolyte and preparation method thereof

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DE10250747A1 (en) * 2002-10-31 2004-05-19 Gaia Akkumulatorenwerke Gmbh Process for production of Li secondary batteries with a cathode composition containing heavy metal oxide, Li-Co oxide, polymer binder, aprotic solvent with complete elimination of electrode water absorption
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
CN103765657A (en) * 2011-06-29 2014-04-30 日东电工株式会社 Nonaqueous-electrolyte secondary battery and positive-electrode sheet therefor
CN103943882A (en) * 2014-03-27 2014-07-23 北京化学试剂研究所 Preparation method of lithium battery electrolyte
WO2015151099A1 (en) * 2014-03-31 2015-10-08 Technion Research & Development Foundation Limited A method for passive metal activation and uses thereof

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DE10250747A1 (en) * 2002-10-31 2004-05-19 Gaia Akkumulatorenwerke Gmbh Process for production of Li secondary batteries with a cathode composition containing heavy metal oxide, Li-Co oxide, polymer binder, aprotic solvent with complete elimination of electrode water absorption
CN103765657A (en) * 2011-06-29 2014-04-30 日东电工株式会社 Nonaqueous-electrolyte secondary battery and positive-electrode sheet therefor
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
CN103943882A (en) * 2014-03-27 2014-07-23 北京化学试剂研究所 Preparation method of lithium battery electrolyte
WO2015151099A1 (en) * 2014-03-31 2015-10-08 Technion Research & Development Foundation Limited A method for passive metal activation and uses thereof

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Address after: 277000 west side of Fuyuan Sixth Road and north of South Ring Road, Xingcheng street, high tech Zone, Zaozhuang City, Shandong Province

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Address before: Huaying Sichuan province 638699 Guang Hua Da Dao SME incubation center four floor, block C

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Address before: 277000 west side of Fuyuan 6th Road, Xingcheng street, high tech Zone, Zaozhuang City, Shandong Province, north of South Ring Road

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