CN111883840B - Flame-retardant electrolyte additive for lithium electronic battery - Google Patents
Flame-retardant electrolyte additive for lithium electronic battery Download PDFInfo
- Publication number
- CN111883840B CN111883840B CN202010770636.XA CN202010770636A CN111883840B CN 111883840 B CN111883840 B CN 111883840B CN 202010770636 A CN202010770636 A CN 202010770636A CN 111883840 B CN111883840 B CN 111883840B
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- China
- Prior art keywords
- electrolyte
- additive
- battery
- flame
- lithium
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000003063 flame retardant Substances 0.000 title claims abstract description 11
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 6
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 239000000654 additive Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000007770 graphite material Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920001774 Perfluoroether Polymers 0.000 abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 6
- 239000011574 phosphorus Substances 0.000 abstract description 6
- 238000004146 energy storage Methods 0.000 abstract description 2
- 239000007774 positive electrode material Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 5
- -1 perfluorinated ether compound Chemical class 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a flame-retardant electrolyte additive and a battery system applicable to the same. The additive is a phosphorus-containing fluoroether derivative, is suitable for a battery system with 50-90 wt% of carbonate solvent in electrolyte, is well matched with the existing lithium battery, does not need to replace a film, a positive electrode material and a shell, and has wide application prospect in the fields of power batteries and energy storage batteries.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage, and relates to a flame-retardant electrolyte additive and a lithium ion battery system suitable for the same.
Background
Lithium ion batteries play an increasingly important role in modern people's life, however batteries are high-density carriers of energy, and intrinsically have unsafe factors; the higher the energy density, the greater the impact of the intense release of energy and the more pronounced the safety problem. When unexpected factors cause thermal runaway, the safety performance of the electrolyte is a key for determining the safety performance of the lithium ion battery.
Compounds containing phosphorus, fluorine, etc., such as phosphites, fluoroethers, etc., can decompose into radicals at high temperatures, combine with hydrogen radicals generated in thermal runaway, and thus block the combustion process. However, the existing perfluorinated ether compound has lower solubility to lithium salt, so that the rate performance of the battery is reduced, while the non-fluorinated ether compound has certain solubility to the lithium salt and has no negative effect on the battery performance, but more than 30wt% of the perfluorinated ether compound is required to be added into the electrolyte to have good flame retardant effect; although the flame retardant performance of the phosphite ester compound to the electrolyte is greatly improved, the addition of the phosphite ester compound causes the working performance of the battery to be reduced by 2-5%.
Accordingly, the inventor proposes the application, wherein the phosphorus-containing fluoroether derivative can achieve the effect of non-combustion of electrolyte under the condition of small dosage in the battery, and has no negative effect on the working performance of the battery.
Disclosure of Invention
In order to overcome the defects, the invention provides the flame-retardant electrolyte additive for the lithium electronic battery, which can effectively improve the safety performance of the battery in a suitable electrolyte system and has no negative effect on the electrochemical performance of the battery.
The technical scheme adopted by the invention for solving the technical problems is as follows: a flame-retardant electrolyte additive for a lithium electronic battery is characterized in that: the additive is a phosphorus-containing fluoroether derivative; is suitable for a lithium ion battery system with 50-90 wt% of carbonate solvent in electrolyte,
the chemical formula of the additive is
Wherein R1, R2 and R3 are each independently H or non-perfluorinated ether substituent containing 3-7 carbon atoms, and each of R1, R2 and R3 is different from the other.
As a further improvement of the invention, the additive is one or a mixture of several phosphorus-containing fluoroether derivatives.
As a further improvement of the invention, the mass proportion of the total amount of the phosphorus-containing fluoroether derivative in the electrolyte is 5-15 wt%.
As a further improvement of the invention, the carbonate solvent in the electrolyte is 50-90 wt%, the negative electrode is made of graphite material, and the working voltage of the battery is not more than 4.35V.
The beneficial effects of the invention are as follows: compared with the existing additive, the additive has the following advantages:
1) The safety is high and the lithium ion battery system is applicable to the lithium ion battery system;
2) The lithium ion battery is in good agreement with the existing lithium ion battery, and a film, a positive electrode material and a shell do not need to be replaced;
3) The safety performance of the battery can be effectively improved, and the working performance of the battery is not negatively influenced;
4) The components of the battery system are clear, and the preparation method is simple;
5) The battery system is suitable for industrial application, and has wide application prospect in the fields of power batteries and energy storage batteries.
Detailed Description
The present invention will be further described in detail with reference to examples, which are provided for the purpose of illustration only and are not intended to limit the scope of the present invention.
Examples:
additive A1:
additive A2:
additive A3:
flame retardant test:
after the electrolyte was prepared in a glove box, the electrolyte was added dropwise to the pp/pe membrane, and the membrane was then ignited to observe the flame-out time.
The test results were as follows:
battery cycle performance test:
the battery capacity used was (NCM 111/graphite) 2.5Ah and the injection rate was 2.8g. After the liquid is injected, the glove box is immediately sealed by a sealing machine, the battery is taken out and is placed at normal temperature for 24 hours, and an electrochemical test is carried out (1C).
The test results are as follows
Claims (2)
1. A flame-retardant electrolyte additive for a lithium electronic battery is characterized in that: the electrolyte is suitable for a lithium ion battery system with 50-90 wt% of carbonate solvent in electrolyte;
the additive is one of the following compounds or a mixture formed by a plurality of the following compounds:
；
the mass proportion of the total additive in the electrolyte is 5-15 wt%.
2. The flame-retardant electrolyte additive for lithium-ion batteries according to claim 1, wherein:
the carbonate solvent in the electrolyte accounts for 50-90 wt%, the negative electrode is made of graphite material, and the working voltage of the battery is not more than 4.35V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010770636.XA CN111883840B (en) | 2020-08-04 | 2020-08-04 | Flame-retardant electrolyte additive for lithium electronic battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010770636.XA CN111883840B (en) | 2020-08-04 | 2020-08-04 | Flame-retardant electrolyte additive for lithium electronic battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111883840A CN111883840A (en) | 2020-11-03 |
| CN111883840B true CN111883840B (en) | 2024-03-05 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010770636.XA Active CN111883840B (en) | 2020-08-04 | 2020-08-04 | Flame-retardant electrolyte additive for lithium electronic battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111883840B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011165606A (en) * | 2010-02-15 | 2011-08-25 | Asahi Kasei E-Materials Corp | Lithium ion secondary battery |
| CN102420340A (en) * | 2011-10-26 | 2012-04-18 | 华为技术有限公司 | Manufacturing method of battery |
| CN102473964A (en) * | 2009-08-04 | 2012-05-23 | 东曹氟技术株式会社 | Asymmetric and/or low-symmetry fluorine-containing phosphate ester for use in a nonaqueous electrolyte solution |
| JP2015065130A (en) * | 2013-09-26 | 2015-04-09 | 旭硝子株式会社 | Nonaqueous electrolytic solution for secondary batteries, and lithium ion secondary battery |
| JP2016045987A (en) * | 2014-08-20 | 2016-04-04 | 株式会社日立製作所 | Electrolytic solution for lithium ion secondary battery, and lithium ion secondary battery |
| KR20170062256A (en) * | 2015-11-27 | 2017-06-07 | 솔브레인 주식회사 | Electrolyte for rechargeable lithium battery and rechargeable lithium battery including the same |
| CN111326799A (en) * | 2020-03-09 | 2020-06-23 | 天津中电新能源研究院有限公司 | Flame-retardant high-voltage electrolyte for lithium ion battery and preparation method thereof |
-
2020
- 2020-08-04 CN CN202010770636.XA patent/CN111883840B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102473964A (en) * | 2009-08-04 | 2012-05-23 | 东曹氟技术株式会社 | Asymmetric and/or low-symmetry fluorine-containing phosphate ester for use in a nonaqueous electrolyte solution |
| JP2011165606A (en) * | 2010-02-15 | 2011-08-25 | Asahi Kasei E-Materials Corp | Lithium ion secondary battery |
| CN102420340A (en) * | 2011-10-26 | 2012-04-18 | 华为技术有限公司 | Manufacturing method of battery |
| JP2015065130A (en) * | 2013-09-26 | 2015-04-09 | 旭硝子株式会社 | Nonaqueous electrolytic solution for secondary batteries, and lithium ion secondary battery |
| JP2016045987A (en) * | 2014-08-20 | 2016-04-04 | 株式会社日立製作所 | Electrolytic solution for lithium ion secondary battery, and lithium ion secondary battery |
| KR20170062256A (en) * | 2015-11-27 | 2017-06-07 | 솔브레인 주식회사 | Electrolyte for rechargeable lithium battery and rechargeable lithium battery including the same |
| CN111326799A (en) * | 2020-03-09 | 2020-06-23 | 天津中电新能源研究院有限公司 | Flame-retardant high-voltage electrolyte for lithium ion battery and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 锂离子电池阻燃添加剂研究;郑洪河, 秦建华, 石磊, 徐仲榆;电池(03);第189-191页 * |
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| Publication number | Publication date |
|---|---|
| CN111883840A (en) | 2020-11-03 |
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| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220112 Address after: 215300 building 6, No. 222, Dechang Road, Shipai, Baicheng Town, Kunshan City, Suzhou City, Jiangsu Province Applicant after: SUZHOU JIANDE YIFANG ENERGY TECHNOLOGY Co.,Ltd. Address before: 215300 building 6, No. 222, Dechang Road, Shipai, Baicheng Town, Kunshan City, Suzhou City, Jiangsu Province Applicant before: Kunshan Hefeng Qinghui Energy Technology Co.,Ltd. |
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