CN111883840A - Flame-retardant electrolyte additive for lithium ion battery - Google Patents
Flame-retardant electrolyte additive for lithium ion battery Download PDFInfo
- Publication number
- CN111883840A CN111883840A CN202010770636.XA CN202010770636A CN111883840A CN 111883840 A CN111883840 A CN 111883840A CN 202010770636 A CN202010770636 A CN 202010770636A CN 111883840 A CN111883840 A CN 111883840A
- Authority
- CN
- China
- Prior art keywords
- lithium ion
- additive
- ion battery
- electrolyte
- flame
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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 15
- 239000003063 flame retardant Substances 0.000 title claims abstract description 15
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 16
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 12
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- 229920001774 Perfluoroether Polymers 0.000 claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical group FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000007770 graphite material Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 abstract description 2
- 239000007774 positive electrode material Substances 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract 1
- 229910052744 lithium Inorganic materials 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- -1 phosphite ester compound Chemical class 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 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
- 230000000903 blocking effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001875 compounds Chemical class 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
- 230000002708 enhancing effect Effects 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
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 238000002360 preparation method Methods 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)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (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 flame-retardant electrolyte additive. The additive is a phosphorus-containing fluoroether derivative, is suitable for a battery system with a carbonate solvent accounting for 50-90 wt% of electrolyte, is in good accordance with the existing lithium battery, does not need to replace a film, a positive electrode material and a shell, and has wide application prospects 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 applicable to the flame-retardant electrolyte additive.
Background
Lithium ion batteries play an increasingly important role in modern people's lives, but the batteries are high-density carriers of energy and have unsafe factors per se; the higher the energy density, the greater the effect of intense release of energy and the more pronounced the safety problem. When heat is out of control due to unexpected factors, the safety performance of the electrolyte is the key for determining the safety performance of the lithium ion battery.
Compounds containing phosphorus, fluorine, etc., such as phosphite esters, fluoroethers, etc., are decomposed into radicals at high temperatures, and combine with hydrogen radicals generated during thermal runaway, thereby blocking the combustion process. However, the existing perfluoro ether compounds have low solubility to lithium salt, so that the rate performance of the battery is reduced, while the non-fluoroether has certain solubility to the lithium salt, so that the battery performance is not negatively affected, but the electrolyte has good flame retardant effect only by adding more than 30 wt%; although the flame retardant performance of the phosphite ester compound to the electrolyte is greatly improved, the working performance of the battery is reduced by 2-5% due to the addition of the phosphite ester compound.
Accordingly, the inventors of the present application propose that the phosphorus-containing fluoroether derivative can achieve the effect of non-combustion of the electrolyte with a small amount of the phosphorus-containing fluoroether derivative 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 ion battery, which can effectively improve the safety performance of the battery in an applicable electrolyte system and has no negative influence on the electrochemical performance of the battery.
The technical scheme adopted by the invention for solving the technical problem is as follows: the flame-retardant electrolyte additive for the lithium ion battery is characterized in that: the additive is a phosphorus-containing fluoroether derivative; is suitable for a lithium ion battery system with carbonate solvent accounting for 50-90 wt% in electrolyte,
the additive has a chemical formula of
Wherein R1, R2 and R3 are respectively H or non-perfluoro ether substituent with carbon content of 3-7, and R1, R2 and R3 are different in pairs.
As a further improvement of the invention, the additive is a mixture of one or more phosphorus-containing fluoroether derivatives.
As a further improvement of the invention, the mass proportion of the total amount of the phosphorus-containing fluoroether derivatives in the electrolyte is 5-15 wt%.
As a further improvement of the invention, the carbonate solvent accounts for 50-90 wt% of the electrolyte, the negative electrode is made of graphite material, and the working voltage of the battery is not more than 4.35V.
The invention has the beneficial effects that: compared with the existing additive, the additive has the following advantages:
1) high safety and suitable for lithium ion battery system;
2) the lithium ion battery has good conformity with the existing lithium ion battery, and does not need to replace a film, a positive electrode material and a shell;
3) the safety performance of the battery can be effectively improved, and the negative influence on the working performance of the battery is avoided;
4) the battery system has clear components and simple preparation method;
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
For the purpose of enhancing understanding of the present invention, the present invention will be further described in detail with reference to the following examples, which are provided for illustration only and are not to be construed as limiting the scope of the present invention.
Example (b):
additive A1:
additive A2:
additive A3:
and (3) flame retardant test:
and (3) dropwise adding the electrolyte into a pp/pe diaphragm after the electrolyte is prepared in the glove box, then igniting the diaphragm, and observing the flame extinguishing time.
The test results were as follows:
and (3) testing the cycle performance of the battery:
the used battery capacity was (NCM 111/graphite) 2.5Ah, and the injection amount was 2.8 g. And immediately sealing the battery in a glove box by using a sealing machine after injection, taking out the battery, standing the battery at normal temperature for 24 hours, and performing electrochemical test (1C).
The test results are as follows
Claims (4)
1. The flame-retardant electrolyte additive for the lithium ion battery is characterized in that: the additive is a phosphorus-containing fluoroether derivative; is suitable for a lithium ion battery system with carbonate solvent accounting for 50-90 wt% in electrolyte,
the additive has a chemical formula of
Wherein R1, R2 and R3 are respectively H or non-perfluoro ether substituent with carbon content of 3-7, and R1, R2 and R3 are different in pairs.
2. A lithium ion battery flame retardant electrolyte additive according to claim 1, characterized in that: the additive is one or a mixture of several phosphorus-containing fluoroether derivatives.
3. A lithium ion battery flame retardant electrolyte additive according to claim 1, characterized in that: the mass proportion of the total amount of the phosphorus-containing fluoroether derivatives in the electrolyte is 5-15 wt%.
4. A lithium ion battery flame retardant electrolyte additive according to claim 1, characterized in that: the carbonate solvent accounts for 50-90 wt% of the electrolyte, the graphite material is adopted as the negative electrode, 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 true CN111883840A (en) | 2020-11-03 |
| CN111883840B CN111883840B (en) | 2024-03-05 |
Family
ID=73210463
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 |
|---|
| 郑洪河, 秦建华, 石磊, 徐仲榆: "锂离子电池阻燃添加剂研究", 电池, no. 03, pages 189 - 191 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111883840B (en) | 2024-03-05 |
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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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