CN113809395A - Electrolyte for lithium battery and lithium battery with same - Google Patents
Electrolyte for lithium battery and lithium battery with same Download PDFInfo
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- CN113809395A CN113809395A CN202111003921.XA CN202111003921A CN113809395A CN 113809395 A CN113809395 A CN 113809395A CN 202111003921 A CN202111003921 A CN 202111003921A CN 113809395 A CN113809395 A CN 113809395A
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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
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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
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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
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides an electrolyte for a lithium battery and a lithium battery with the same. The electrolyte for a lithium battery includes an organic solvent including: at least one chain carboxylate compound, and at least one phosphite compound. The electrolyte for lithium batteries provided by the invention can show excellent performance even in a low-temperature environment.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to an electrolyte for a lithium battery and a lithium battery with the same.
Background
In the 21 st century, lithium batteries are widely used in various fields such as mobile phones, computers, wearable devices, electric automobiles, two-wheel bicycles, electric tools, street lamps and the like.
In recent years, with the wider application of lithium batteries in various fields, the requirements on the performance and the application environment of the batteries are higher and higher, such as high-power discharge, ultralow-temperature discharge below-30 ℃, 10000 times of ultra-long cycle life and the like. Particularly in the low-temperature field, the demand becomes more and more vigorous, however, under the low-temperature condition, firstly, the discharge of the lithium battery becomes more and more difficult or even impossible along with the reduction of the temperature; and secondly, under the condition of low-temperature charging, the constant current rush-in ratio of the battery is very low, namely the battery cannot be charged, lithium is easy to separate out from the negative electrode during low-temperature charging, and the battery after lithium separation is easy to spontaneously combust or explode, so that safety accidents are caused.
The conventional lithium battery electrolyte mainly comprises an organic solvent and a lithium salt, wherein the common organic solvent is a mixture of cyclic carbonate and chain carbonate, the cyclic carbonate is one or more than two of ethylene carbonate, propylene carbonate and butylene carbonate, and the chain carbonate is one or more than two of dimethyl carbonate, diethyl carbonate and methylethyl carbonate. Below-30 c, the electrolyte prepared from the above organic solvent system and lithium salt is in a near-solidified state or a solidified state, and a lithium battery using the above electrolyte is basically inoperable.
Disclosure of Invention
An object of the present invention is to provide an electrolyte for a lithium battery, comprising an organic solvent, the organic solvent comprising: at least one chain carboxylate compound, and at least one phosphite compound.
As the known technology, the problem that the mobility of lithium ions in electrolyte and an SEI film is difficult to transfer due to the fact that the chain carboxylate compound and the phosphite ester compound are simultaneously introduced into the electrolyte for the lithium battery is solved; meanwhile, the chain carboxylate compound and the phosphite ester compound act synergistically to generate a large amount of li on the surface of the negative electrode3P、li5P, LiF and the like, and Li3P、li5P, LiO the lithium ion permeability and electron conductivity are much better than other components in SEI, such as lithium alkyl carbonate and Li2CO3(ii) a Furthermore, the chain carboxylate compound and the phosphite ester compound can prevent the redox reaction between the positive electrode material and the organic solvent caused by the polarization increase of the lithium battery under the low temperature condition, thereby prolonging the cycle life of the lithium battery. Therefore, the lithium battery adopting the electrolyte has better low-temperature performance.
In a preferred embodiment of the present invention, the chain carboxylate compound is one or more selected from the group consisting of methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, and propyl butyrate.
In a preferred embodiment of the present invention, the phosphite compound is one or more selected from the group consisting of trimethyl phosphite, triethyl phosphite, triisopropyl phosphite, tri-n-propyl phosphite, triphenyl phosphite, tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triphenyl phosphite, trivinyl phosphite, and triallyl phosphite.
In a preferred embodiment of the present invention, the organic solvent further contains a cyclic carbonate compound and a chain carbonate compound; in the organic solvent, the mass ratio of the cyclic carbonate compound to the chain carboxylate compound to the phosphite compound is 10-20: 30-50: 5-30. The invention discovers that the conventional cyclic carbonate compound and chain carbonate compound are compounded to be used as an organic solvent, the prepared electrolyte can be applied to the environment with the temperature of more than 10 ℃ below zero, the performance is obviously reduced at lower temperature, and if only the chain carboxylate compound and the phosphite ester compound are used as the organic solvent, although the low-temperature performance is excellent, the solubility of the solvent to lithium salt is poor, thereby affecting the performance of the electrolyte. By compounding the cyclic carbonate compound, the chain carboxylate compound and the phosphite ester compound in the above proportions, the solubility of lithium salt and the low-temperature performance can be optimally considered.
In a preferred embodiment of the present invention, the cyclic carbonate compound is selected from ethylene carbonate and/or propylene carbonate.
In a preferred embodiment of the present invention, the chain carbonate compound is one or more selected from the group consisting of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dipropyl carbonate, and methyl propyl carbonate.
In a preferred embodiment of the present invention, the electrolyte further comprises a composite additive, wherein the composite additive comprises vinylene carbonate and other additives, and the other additives are selected from one or more of methylene methane disulfonate, lithium difluorophosphate and lithium difluorooxalato borate. The invention discovers that the methylene methanedisulfonate, the lithium difluorophosphate and the lithium difluorooxalato borate can act with vinylene carbonate synergistically, so that the film forming effect of the lithium battery is improved, the impedance is reduced, and the conduction speed of electrons and ions at low temperature is improved, thereby improving the low-temperature charge and discharge performance of the lithium ion battery.
In a further preferred embodiment, the mass ratio of the vinylene carbonate to the other additives is 1:1 to 1: 3.
The electrolyte also comprises a lithium salt, and in a preferred embodiment, the mass ratio of the organic solvent to the lithium salt to the composite additive is 78-87.8: 12-20: 0.2-2.
In a further preferred embodiment, the lithium salt is selected from one or two or more of lithium hexafluorophosphate, lithium perchlorate and lithium tetrafluoroborate.
The present invention also provides a lithium battery comprising at least the above-described electrolyte for a lithium battery, a positive electrode and a negative electrode.
According to the present invention, an electrolyte for a lithium battery that can exhibit excellent performance even in a low-temperature environment, and a lithium battery including the same can be provided.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications.
In the following examples, the equipment and the like used are not shown to manufacturers, and are all conventional products available from regular vendors. The process is conventional unless otherwise specified, and the starting materials are commercially available from the open literature.
Example 1
Embodiment 1 provides an electrolyte for a lithium battery, comprising the steps of:
(1) 12.435g of ethylene carbonate, 14.922g of methyl ethyl carbonate, 33.160g of propyl propionate and 22.383g of trimethyl phosphite are uniformly mixed to obtain an organic solvent (the mass percentage of the four is 15:18:40: 27);
(2) adding 15.6g of lithium hexafluorophosphate, 0.5g of vinylene carbonate and 1g of lithium difluorooxalato borate into 82.9g of organic solvent, and uniformly mixing to obtain the electrolyte.
Example 2
Embodiment 2 provides an electrolyte for a lithium battery, including the steps of:
(1) 15.640g of ethylene carbonate, 15.640g of methyl ethyl carbonate, 39.100g of ethyl propionate and 7.820g of triethyl phosphite are uniformly mixed to obtain an organic solvent (the mass percentage of the four is 20:20:50: 10);
(2) adding 20g of lithium hexafluorophosphate, 0.5g of vinylene carbonate and 1.3g of methylene methyl disulfonate into 78.2g of organic solvent, and uniformly mixing to obtain the electrolyte.
Example 3
Embodiment 3 provides an electrolyte for a lithium battery, comprising the steps of:
(1) 12.800g of ethylene carbonate, 15.200g of dimethyl carbonate, 36.000g of propyl propionate and 16.000g of trimethyl phosphite are uniformly mixed to obtain an organic solvent (the mass percentage of the four is 16:19:45: 20);
(2) adding 18.0g of lithium hexafluorophosphate, 0.5g of vinylene carbonate and 1.5g of lithium difluorophosphate into 80.0g of organic solvent, and uniformly mixing to obtain the electrolyte.
Example 4
Embodiment 4 provides an electrolyte for a lithium battery, comprising the steps of:
(1) uniformly mixing 15.66g of ethylene carbonate, 15.66g of methyl ethyl carbonate, 43.50g of propyl propionate and 12.18g of triphenyl phosphite to obtain an organic solvent (the mass percentage of the four is 18:18:50: 14);
(2) adding 12g of lithium hexafluorophosphate, 0.3g of vinylene carbonate, 0.3g of lithium difluorooxalato borate and 0.4g of methylene methanedisulfonate into 87.0g of an organic solvent, and uniformly mixing to obtain the electrolyte.
Comparative example 1
Comparative example 1 provides an electrolyte for a lithium battery, comprising the steps of:
(1) 27.633g of ethylene carbonate, 27.633g of methyl ethyl carbonate and 27.634g of dimethyl carbonate are uniformly mixed to obtain an organic solvent;
(2) adding 15.6g of lithium hexafluorophosphate, 0.5g of vinylene carbonate and 1g of lithium difluorooxalato borate into 82.9g of organic solvent, and uniformly mixing to obtain the electrolyte.
Comparative example 2
Comparative example 2 provides an electrolyte for a lithium battery, comprising the steps of:
(1) 26.066g of ethylene carbonate, 26.066g of methyl ethyl carbonate and 26.067g of dimethyl carbonate are uniformly mixed to obtain an organic solvent;
(2) adding 20g of lithium hexafluorophosphate, 0.5g of vinylene carbonate and 1.3g of methylene methyl disulfonate into 78.2g of organic solvent, and uniformly mixing to obtain the electrolyte.
Comparative example 3
Comparative example 3 provides an electrolyte for a lithium battery, comprising the steps of:
(1) uniformly mixing 26.666g of ethylene carbonate, 26.666g of methyl ethyl carbonate and 26.667g of dimethyl carbonate to obtain an organic solvent;
(2) adding 18.0g of lithium hexafluorophosphate, 0.5g of vinylene carbonate and 1.5g of lithium difluorophosphate into 80.0g of organic solvent, and uniformly mixing to obtain the electrolyte.
Comparative example 4
Comparative example 4 provides an electrolyte for a lithium battery, comprising the steps of:
(1) uniformly mixing 29.0g of ethylene carbonate, 29.0g of methyl ethyl carbonate and 29.0g of dimethyl carbonate to obtain an organic solvent;
(2) adding 12g of lithium hexafluorophosphate, 0.3g of vinylene carbonate, 0.3g of lithium difluorooxalato borate and 0.4g of methylene methanedisulfonate into 87.0g of an organic solvent, and uniformly mixing to obtain the electrolyte.
Comparative example 5
Comparative example 5 provides an electrolyte for a lithium battery, comprising the steps of:
(1) 12.435g of ethylene carbonate, 14.922g of methyl ethyl carbonate, 33.160g of dimethyl carbonate and 22.383g of trimethyl phosphite are uniformly mixed to obtain an organic solvent (the mass percentage of the four is 15:18:40: 27);
(2) adding 15.6g of lithium hexafluorophosphate, 0.5g of vinylene carbonate and 1g of lithium difluorooxalato borate into 82.9g of organic solvent, and uniformly mixing to obtain the electrolyte.
Comparative example 6
Comparative example 6 provides an electrolyte for a lithium battery, comprising the steps of:
(1) 12.435g of ethylene carbonate, 14.922g of methyl ethyl carbonate, 33.160g of propyl propionate and 22.383g of dimethyl carbonate are uniformly mixed to obtain an organic solvent (the mass percentage of the four is 15:18:40: 27);
(2) adding 15.6g of lithium hexafluorophosphate, 0.5g of vinylene carbonate and 1g of lithium difluorooxalato borate into 82.9g of organic solvent, and uniformly mixing to obtain the electrolyte.
Test examples Low temperature Performance test
The electrolytes for lithium batteries prepared in examples 1 to 4 and comparative examples 1 to 6 were injected into 26650 to 4.0Ah cells (positive electrode lithium iron phosphate, negative electrode graphite) to prepare batteries.
(1) Respectively charging the prepared battery at a multiplying power of 0.2C at the temperature of minus 20 ℃, charging at a multiplying power of 0.5C at the temperature of minus 40 ℃, and recording constant current charging ratio data during charging;
(2) the prepared battery was subjected to a 1C/1C charge-discharge cycle test at-20 ℃, and the capacity retention rate was recorded after 300 cycles, with the results shown in Table 1 below.
TABLE 1
As is clear from Table 1, it was confirmed that the constant current rush-in ratio of the lithium battery using the electrolyte solutions of examples 1 to 4 was more than 98% in the low temperature environment of-20 ℃ and was still more than 84% even in the low temperature environment of-40 ℃ and the electrolyte solution was excellent in the low temperature double charging performance. Meanwhile, the lithium battery is circularly charged and discharged for 300 times at the low temperature of-20 ℃, the capacity retention rate of the lithium battery using the electrolyte of the embodiment 1-4 is more than 92%, and the low-temperature circulation performance of the electrolyte is excellent.
Finally, the method of the present invention is only a preferred embodiment and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An electrolyte for a lithium battery, characterized in that it comprises an organic solvent comprising: at least one chain carboxylate compound, and at least one phosphite compound.
2. The electrolyte for a lithium battery according to claim 1, wherein the chain carboxylate compound is one or more selected from methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, and propyl butyrate.
3. The electrolyte for a lithium battery according to claim 1 or 2, wherein the phosphite compound is one or more selected from the group consisting of trimethyl phosphite, triethyl phosphite, triisopropyl phosphite, tri-n-propyl phosphite, triphenyl phosphite, tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triphenyl phosphite, trivinyl phosphite, and triallyl phosphite.
4. The electrolyte for a lithium battery according to any one of claims 1 to 3, wherein the organic solvent further contains a cyclic carbonate compound and a chain carbonate compound; the mass ratio of the cyclic carbonate compound to the chain carboxylate compound to the phosphite compound is 10-20: 30-50: 5-30.
5. The electrolyte for a lithium battery according to claim 4, wherein the cyclic carbonate compound is selected from ethylene carbonate and/or propylene carbonate;
and/or the chain carbonate compound is one or more selected from dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dipropyl carbonate and methyl propyl carbonate.
6. The electrolyte for a lithium battery according to any one of claims 1 to 5, further comprising a composite additive, the composite additive comprising vinylene carbonate and other additives, the other additives being selected from one or more of methylene methanedisulfonate, lithium difluorophosphate and lithium difluorooxalato borate.
7. The electrolyte for a lithium battery according to claim 6, wherein the mass ratio of the vinylene carbonate to the other additives in the composite additive is 1:1 to 1: 3.
8. The electrolyte for a lithium battery according to any one of claims 1 to 7, further comprising a lithium salt, wherein the mass ratio of the organic solvent, the lithium salt and the composite additive is 78 to 87.8:12 to 20:0.2 to 2.
9. The electrolyte for a lithium battery according to claim 8, wherein the lithium salt is one or two or more selected from the group consisting of lithium hexafluorophosphate, lithium perchlorate, and lithium tetrafluoroborate.
10. A lithium battery comprising at least the electrolyte for a lithium battery according to any one of claims 1 to 9, a positive electrode, and a negative electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111003921.XA CN113809395A (en) | 2021-08-30 | 2021-08-30 | Electrolyte for lithium battery and lithium battery with same |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111003921.XA CN113809395A (en) | 2021-08-30 | 2021-08-30 | Electrolyte for lithium battery and lithium battery with same |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107666011A (en) * | 2016-07-28 | 2018-02-06 | 微宏动力系统（湖州）有限公司 | A kind of nonaqueous electrolytic solution and nonaqueous electrolytic solution secondary battery |
| CN107732163A (en) * | 2016-08-12 | 2018-02-23 | 微宏动力系统（湖州）有限公司 | A kind of lithium rechargeable battery |
| CN110444810A (en) * | 2018-05-04 | 2019-11-12 | 宁德时代新能源科技股份有限公司 | Electrolyte solution and secondary battery |
| CN111116659A (en) * | 2018-10-31 | 2020-05-08 | 张家港市国泰华荣化工新材料有限公司 | Compound, electrolyte and lithium ion battery |
| CN111116651A (en) * | 2019-12-31 | 2020-05-08 | 天目湖先进储能技术研究院有限公司 | Phosphite ester compound containing thienyl and application thereof |
-
2021
- 2021-08-30 CN CN202111003921.XA patent/CN113809395A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107666011A (en) * | 2016-07-28 | 2018-02-06 | 微宏动力系统（湖州）有限公司 | A kind of nonaqueous electrolytic solution and nonaqueous electrolytic solution secondary battery |
| CN107732163A (en) * | 2016-08-12 | 2018-02-23 | 微宏动力系统（湖州）有限公司 | A kind of lithium rechargeable battery |
| CN110444810A (en) * | 2018-05-04 | 2019-11-12 | 宁德时代新能源科技股份有限公司 | Electrolyte solution and secondary battery |
| CN111116659A (en) * | 2018-10-31 | 2020-05-08 | 张家港市国泰华荣化工新材料有限公司 | Compound, electrolyte and lithium ion battery |
| CN111116651A (en) * | 2019-12-31 | 2020-05-08 | 天目湖先进储能技术研究院有限公司 | Phosphite ester compound containing thienyl and application thereof |
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