CN112909339A - Propylene carbonate-based electrolyte and lithium ion battery containing same - Google Patents
Propylene carbonate-based electrolyte and lithium ion battery containing same Download PDFInfo
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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Abstract
The invention discloses a propylene carbonate-based electrolyte and a lithium ion battery containing the same. The diluent is one or more of trimethyl borate, triethyl borate, tripropyl borate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl butyl ether, ethyl butyl ether, propyl butyl ether, methyl ethyl ether and ethylene glycol dimethyl ether. The propylene carbonate-based electrolyte and the lithium ion battery containing the same have the characteristics of high conductivity, excellent low-temperature performance and good high-voltage stability.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a propylene carbonate-based electrolyte and a lithium ion battery containing the same.
Background
The lithium ion battery has the advantages of high energy density, high working voltage, long cycle life, no memory effect and the like, and is widely applied to the fields of portable electronic equipment, electric automobiles, large-scale energy storage and the like. Nowadays, people have higher requirements on the energy density of lithium ion batteries; in addition, low-temperature charge and discharge performance of lithium ion batteries is also receiving attention.
Currently, the components of commercial lithium ion battery electrolytes are composed of lithium hexafluorophosphate as lithium salt, high viscosity and high freezing point (> 35 ℃) ethylene carbonate as solvent, and a part of chain carbonate solvent. The ethylene carbonate can generate a compact and effective SEI film on the surface of the lithium ion battery cathode in the charge and discharge processes, so that the ethylene carbonate becomes an essential part of the electrolyte. However, the application of high-voltage cathode materials is limited due to the property that ethylene carbonate cannot withstand high voltage, and the voltage of more than 4.3V can cause the continuous oxidative decomposition and gas generation of the ethylene carbonate, so that the internal resistance of the battery is increased, and the capacity of the battery is rapidly reduced. In addition, the high viscosity and high freezing point of ethylene carbonate make the electrolyte rapidly decrease in conductivity at low temperature and easily freeze, which is very disadvantageous for charging and discharging the battery at low temperature.
The propylene carbonate is used as a solvent similar to ethylene carbonate, has high dielectric constant, can fully dissociate lithium salt, has better high-voltage resistance and lower freezing point (-48.8 ℃) and is more favorable for the application of high-voltage anode materials and the low-temperature charge and discharge performance of batteries. However, propylene carbonate cannot form a dense SEI film on the surface of the lithium ion battery negative electrode, and is continuously reduced and decomposed, so that the propylene carbonate cannot be applied to the lithium ion battery electrolyte. Recently, a high concentration lithium salt electrolyte is reported to have excellent reduction stability, making practical use of propylene carbonate possible. In the high-concentration lithium salt electrolyte, almost all the molecules of the propylene carbonate solvent are complexed with lithium ions, and only a small amount of free solvent molecules exist, so that the activity of the solvent is greatly reduced, the reduction stability of the propylene carbonate is greatly enhanced, and the compatibility of the propylene carbonate and a commercialized negative electrode is realized. However, the high concentration lithium salt electrolyte has extremely high viscosity, low electrical conductivity and expensive price, which is very disadvantageous for commercial application of such electrolyte.
The non-polar solvents which are not coordinated with lithium ions, such as fluoroether, halogenated alkane and the like, are added into the high-concentration lithium salt electrolyte to form a local high-concentration electrolyte, so that the concentration and viscosity of the lithium salt of the electrolyte can be effectively reduced, but the non-polar solvents are not complexed with the lithium ions, the dissociation concentration of the lithium salt cannot be increased, and the problem of low conductivity of the high-concentration electrolyte cannot be solved. In addition, the boiling point of the nonpolar solvents is only 30-60 ℃ generally, and the nonpolar solvents are extremely volatile, so that the problems of accurate preparation of the electrolyte and air inflation in the use process of the lithium ion battery are extremely unfavorable.
Disclosure of Invention
The invention aims to provide a propylene carbonate-based electrolyte and a lithium ion battery containing the same, which have the characteristics of high conductivity, excellent low-temperature performance and good high-voltage stability.
The invention can be realized by the following technical scheme:
the invention discloses a propylene carbonate-based electrolyte, which comprises a propylene carbonate solvent, lithium salt and a diluent, wherein the diluent is a weak-polarity chain solvent.
In the invention, the diluent is a low-polarity chain solvent, so that the coordination structure of propylene carbonate and lithium ions is not changed, the characteristic of high stability of the propylene carbonate-based electrolyte is reserved, and the dissociation degree of the lithium ions can be increased, thereby greatly improving the conductivity of the electrolyte.
In the present invention, the propylene carbonate-based electrolyte is composed of two parts: propylene carbonate solvent of high concentration lithium salt; (ii) a weakly polar but not a non-polar diluent. In the propylene carbonate solvent of high-concentration lithium salt, the molecules of the propylene carbonate solvent are coordinated with lithium ions, only a small amount of free propylene carbonate solvent molecules exist, and the reaction activity of the propylene carbonate is greatly reduced, so that the propylene carbonate has excellent redox stability, has good compatibility with positive and negative electrode materials of a lithium ion battery, but has high viscosity, low electrical conductivity and high lithium salt concentration. The diluent is a weak-polarity rather than non-polar solvent, so that most of the diluent is a chain solvent, the coordination capacity of the diluent is weak, and the position of propylene carbonate in a lithium ion solvation structure cannot be replaced after the propylene carbonate electrolyte with high-concentration lithium salt is added, so that the redox stability of the propylene carbonate cannot be influenced, but the viscosity of the electrolyte can be effectively reduced, the dissociation degree of the lithium salt is increased, and the conductivity of the electrolyte is improved.
Further, the diluent is one or more of trimethyl borate, triethyl borate, tripropyl borate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl butyl ether, ethyl butyl ether, propyl butyl ether, methyl ethyl ether and ethylene glycol dimethyl ether.
Furthermore, the volume ratio of the propylene carbonate solvent in the propylene carbonate-based electrolyte is 10-80%, and the volume ratio of the diluent in the propylene carbonate-based electrolyte is 20-90%.
Further, in the propylene carbonate-based electrolyte, the concentration of the lithium salt is 0.5 to 5 mol/L.
Further, the propylene carbonate-based electrolyte may further include a film forming additive to enhance electrolyte/electrode interface stability.
Furthermore, the film forming additive is one or more of fluoroethylene carbonate, vinylene sulfate, lithium difluorophosphate and lithium bis (oxalato) borate, and the addition amount of the film forming additive is 0.1-10 wt% of the total mass of the propylene carbonate-based electrolyte.
Further, the lithium salt is one or more than two of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bis (fluorosulfonyl) imide, lithium trifluoromethane sulfonate, lithium bis (trifluoromethanesulfonyl) imide and lithium bis (fluorooxalato) borate.
Another aspect of the present invention is to provide a lithium ion battery comprising the above-described propylene carbonate-based electrolyte.
Further, the lithium ion battery is a cylindrical lithium ion battery, a soft package lithium ion battery or an aluminum shell lithium ion battery.
Further, the lithium ion battery is a lithium iron phosphate lithium ion battery, a lithium cobalt oxide lithium ion battery, a lithium manganate lithium ion battery, a nickel cobalt manganese ternary lithium ion battery or a nickel cobalt aluminum ternary lithium ion battery.
The invention relates to a propylene carbonate-based electrolyte and a lithium ion battery containing the same, which have the following beneficial effects:
the propylene carbonate-based electrolyte and the lithium ion battery have excellent electrochemical properties, do not contain ethylene carbonate, and have good low-temperature performance and high voltage stability because the main solvent is propylene carbonate, so that the propylene carbonate-based electrolyte and the lithium ion battery are suitable for the lithium ion battery and the low-temperature lithium ion battery with high energy density;
secondly, the conductivity is high, and by adding the weak-polarity diluent, the reduction stability of the propylene carbonate electrolyte of high-concentration lithium salt is maintained, the dissociation degree of the lithium salt is increased, the viscosity of the electrolyte is reduced, and the conductivity of the electrolyte is greatly improved. .
Drawings
Fig. 1 is a first cycle charge and discharge curve of a graphite negative electrode in an ethyl butyl ether diluted propylene carbonate electrolyte of a high concentration lithium salt and a propylene carbonate electrolyte of a high concentration lithium salt in application example 1 of the present invention.
FIG. 2 shows LiNi in example 2 of application of the present invention0.6Co0.2Mn0.2O2The cycling performance of the ternary positive electrode was compared in a propylene carbonate electrolyte and a vinyl carbonate-based electrolyte of a high concentration lithium salt diluted with diethyl carbonate.
FIG. 3 shows the present inventionUsing LiNi from example 30.5Co0.2Mn0.3O2The cycling performance of the graphite soft package battery in a propylene carbonate electrolyte and a vinyl carbonate-based electrolyte of high-concentration lithium salt diluted by methyl butyl ether is compared.
FIG. 4 shows LiNi in example 4 of application of the present invention0.5Co0.2Mn0.3O2Low temperature discharge performance of graphite pouch cell in ethylene carbonate based electrolyte.
FIG. 5 shows LiNi in example 4 of application of the present invention0.5Co0.2Mn0.3O2The low-temperature discharge performance of the graphite soft package battery in a propylene carbonate electrolyte of high-concentration lithium salt diluted by propyl butyl ether is improved.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the following detailed description of the present invention is provided with reference to the accompanying drawings.
The invention discloses a propylene carbonate-based electrolyte, which comprises a propylene carbonate solvent, lithium salt and a diluent, wherein the diluent is a weak-polarity chain solvent.
Further, the diluent is one or more of trimethyl borate, triethyl borate, tripropyl borate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl butyl ether, ethyl butyl ether, propyl butyl ether, methyl ethyl ether and ethylene glycol dimethyl ether.
Furthermore, the volume ratio of the propylene carbonate solvent in the propylene carbonate-based electrolyte is 10-80%, and the volume ratio of the diluent in the propylene carbonate-based electrolyte is 20-90%.
Further, in the propylene carbonate-based electrolyte, the concentration of the lithium salt is 0.5 to 5 mol/L.
Further, the propylene carbonate-based electrolyte also includes a film forming additive.
Furthermore, the film forming additive is one or more of fluoroethylene carbonate, vinylene sulfate, lithium difluorophosphate and lithium bis (oxalato) borate, and the addition amount of the film forming additive is 0.1-10 wt% of the total mass of the propylene carbonate-based electrolyte.
Further, the lithium salt is one or more than two of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bis (fluorosulfonyl) imide, lithium trifluoromethane sulfonate, lithium bis (trifluoromethanesulfonyl) imide and lithium bis (fluorooxalato) borate.
Another aspect of the present invention is to provide a lithium ion battery comprising the above-described propylene carbonate-based electrolyte.
Further, the lithium ion battery is a cylindrical lithium ion battery, a soft package lithium ion battery or an aluminum shell lithium ion battery.
Further, the lithium ion battery is a lithium iron phosphate lithium ion battery, a lithium cobalt oxide lithium ion battery, a lithium manganate lithium ion battery, a nickel cobalt manganese ternary lithium ion battery or a nickel cobalt aluminum ternary lithium ion battery.
Example 1
The invention discloses a propylene carbonate-based electrolyte, which comprises a propylene carbonate solvent, lithium salt and a diluent, wherein the diluent is a weak-polarity chain solvent.
In this example, the diluent is trimethyl borate or triethyl borate. The volume ratio of the propylene carbonate solvent in the propylene carbonate-based electrolyte is 60%, and the volume ratio of the diluent in the propylene carbonate-based electrolyte is 40%. In the propylene carbonate-based electrolyte, the concentration of the lithium salt was 5 mol/L. The lithium salt is lithium hexafluorophosphate.
Example 2
The invention discloses a propylene carbonate-based electrolyte, which comprises a propylene carbonate solvent, lithium salt and a diluent, wherein the diluent is a weak-polarity chain solvent.
In this example, the diluent is tripropyl borate, dimethyl carbonate, diethyl carbonate. The volume ratio of the propylene carbonate solvent in the propylene carbonate-based electrolyte is 35%, and the volume ratio of the diluent in the propylene carbonate-based electrolyte is 65%. In the propylene carbonate-based electrolyte, the concentration of the lithium salt was 4 mol/L. The lithium salt is lithium bistrifluoromethylsulfonyl imide.
Example 3
The invention discloses a propylene carbonate-based electrolyte, which comprises a propylene carbonate solvent, lithium salt and a diluent, wherein the diluent is a weak-polarity chain solvent.
In this example, the diluent is ethylbutyl ether, propylbutyl ether, methylethyl ether, ethylene glycol dimethyl ether. The volume ratio of the propylene carbonate solvent in the propylene carbonate-based electrolyte is 10%, and the volume ratio of the diluent in the propylene carbonate-based electrolyte is 90%. In the propylene carbonate-based electrolyte, the concentration of the lithium salt was 2.5 mol/L. The lithium salt is lithium hexafluorophosphate.
Example 4
The invention discloses a propylene carbonate-based electrolyte, which comprises a propylene carbonate solvent, lithium salt and a diluent, wherein the diluent is a weak-polarity chain solvent.
In this example, the diluent is trimethyl borate, triethyl borate, tripropyl borate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl butyl ether. The volume ratio of the propylene carbonate solvent in the propylene carbonate-based electrolyte is 30%, and the volume ratio of the diluent in the propylene carbonate-based electrolyte is 70%. In the propylene carbonate-based electrolyte, the concentration of the lithium salt was 3 mol/L. The lithium salt is lithium bis (fluorooxalato) borate.
Example 5
The invention discloses a propylene carbonate-based electrolyte, which comprises a propylene carbonate solvent, lithium salt and a diluent, wherein the diluent is a weak-polarity chain solvent.
In this example, the diluent was trimethyl borate. The volume ratio of the propylene carbonate solvent in the propylene carbonate-based electrolyte is 20%, and the volume ratio of the diluent in the propylene carbonate-based electrolyte is 80%. In the propylene carbonate-based electrolyte, the concentration of the lithium salt was 4.5 mol/L. The lithium salt is lithium perchlorate, lithium bis (fluorosulfonyl) imide and the like.
In this embodiment, the propylene carbonate-based electrolyte further includes a film forming additive. The film forming additive is fluoroethylene carbonate, and the addition amount of the film forming additive is 5 wt% of the total mass of the propylene carbonate-based electrolyte.
Example 6
The invention discloses a propylene carbonate-based electrolyte, which comprises a propylene carbonate solvent, lithium salt and a diluent, wherein the diluent is a weak-polarity chain solvent.
In this example, the diluent is trimethyl borate, triethyl borate, diethyl carbonate, ethyl methyl carbonate. The volume ratio of the propylene carbonate solvent in the propylene carbonate-based electrolyte is 50%, and the volume ratio of the diluent in the propylene carbonate-based electrolyte is 50%. In the propylene carbonate-based electrolyte, the concentration of the lithium salt was 3.5 mol/L. The lithium salt is lithium bis (fluorosulfonyl) imide or lithium trifluoromethanesulfonate.
In this embodiment, the propylene carbonate-based electrolyte further includes a film forming additive. The film forming additive is fluoroethylene carbonate, and the addition amount of the film forming additive is 3 wt% of the total mass of the propylene carbonate-based electrolyte.
Example 7
The invention discloses a propylene carbonate-based electrolyte, which comprises a propylene carbonate solvent, lithium salt and a diluent, wherein the diluent is a weak-polarity chain solvent.
In this example, the diluent is trimethyl borate, ethylbutyl ether, propylbutyl ether, methylethyl ether. The volume ratio of the propylene carbonate solvent in the propylene carbonate-based electrolyte is 40%, and the volume ratio of the diluent in the propylene carbonate-based electrolyte is 60%. In the propylene carbonate-based electrolyte, the concentration of the lithium salt was 4 mol/L. The lithium salt is lithium hexafluorophosphate.
In this embodiment, the propylene carbonate-based electrolyte further includes a film forming additive. The film forming additive is fluoroethylene carbonate and vinylene carbonate, and the addition amount of the film forming additive is 0.2 wt% of the total mass of the propylene carbonate-based electrolyte.
Application example 1
Preparing 3mol/L lithium bis (fluorosulfonyl) imide/propylene carbonate electrolyte in a glove box filled with argon, and mixing the electrolyte with ethyl butyl ether according to a volume ratio of 1: 1.5, uniformly mixing to obtain a propylene carbonate electrolyte of a high-concentration lithium salt diluted by ethyl butyl ether, and adding 1 wt% of fluoroethylene carbonate into the electrolyte. A graphite cathode and a lithium sheet are used for assembling a CR2032 button type half cell, and the electrochemical performances of the graphite cathode in a propylene carbonate electrolyte with high-concentration lithium salt and the diluted electrolyte are respectively tested. It can be seen that the graphite negative electrode has less polarization and higher reversible specific capacity in the diluted electrolyte because the diluted electrolyte has lower viscosity and higher conductivity. This example demonstrates that the diluted electrolyte still has similar reduction stability to the high concentration lithium salt electrolyte.
Application example 2
Preparing 4mol/L lithium hexafluorophosphate/propylene carbonate electrolyte in a glove box filled with argon, and mixing the electrolyte with diethyl carbonate according to the volume ratio of 1: 2, uniformly mixing to obtain the propylene carbonate electrolyte of high-concentration lithium salt diluted by diethyl carbonate. Using LiNi0.6Co0.2Mn0.2O2Assembling a ternary positive electrode and a lithium sheet into a CR2032 button type half cell, and respectively testing the electrochemical performances of the ternary positive electrode in diluted propylene carbonate electrolyte and 1mol/L lithium hexafluorophosphate/ethylene carbonate-dimethyl carbonate-ethyl methyl carbonate (volume ratio is 1: 1: 1) electrolyte. It can be seen that the ternary positive electrode has good cycling stability in the diluted propylene carbonate electrolyte, and the capacity of 99.1% is maintained after the ternary positive electrode is cycled for 100 weeks in a voltage interval of 2.8-4.6V, which is far higher than the capacity retention rate of 47.0% in the ethylene carbonate-based electrolyte.
Application example 3
Preparing 4mol/L lithium bistrifluoromethylsulfonyl imide/propylene carbonate electrolyte in a glove box filled with argon, and mixing the electrolyte with methyl butyl ether according to the volume ratio of 1: 1, and uniformly mixing to obtain the propylene carbonate electrolyte of high-concentration lithium salt diluted by methyl butyl ether. The electrolyte and 1mol/L of lithium hexafluorophosphate/ethylene carbonate-dimethyl carbonate-ethyl methyl carbonate (volume ratio 1: 1: 1) electrolyte are respectively injected into LiNi0.5Co0.2Mn0.3O2And testing the cycle performance in the soft package battery assembled by the ternary positive electrode and the graphite negative electrode. It can be seen that the diluted propylene carbonate electrolyte has better stability, the capacity retention rate is 99.7% after the diluted propylene carbonate electrolyte is circulated for 100 weeks in a voltage range of 3.0V-4.2V, almost no attenuation is caused, and the capacity retention rate is obviously superior to 96.9% of that of a vinyl carbonate electrolyte.
Application example 4
Under the condition of filling with argonPreparing 4mol/L lithium hexafluorophosphate/propylene carbonate electrolyte in a glove box, and mixing the electrolyte with propyl butyl ether according to the volume ratio of 1: 2, uniformly mixing to obtain the propylene carbonate electrolyte of high-concentration lithium salt diluted by propyl butyl ether. The electrolyte and 1mol/L of lithium hexafluorophosphate/ethylene carbonate-dimethyl carbonate-ethyl methyl carbonate (volume ratio 1: 1: 1) electrolyte are respectively injected into LiNi0.5Co0.2Mn0.3O2And testing the low-temperature discharge performance in the soft package battery assembled by the ternary positive electrode and the graphite negative electrode. The discharge performance of the soft package battery of the diluted propylene carbonate electrolyte at various low temperatures under the current of 0.2C is far better than that of the ethylene carbonate electrolyte, and the soft package battery can still discharge 58.9 percent of discharge capacity at normal temperature even at the temperature of minus 30 ℃, while the ethylene carbonate electrolyte has almost no discharge capacity.
The above embodiments are only specific embodiments of the present invention, and the description thereof is specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications are possible without departing from the inventive concept, and such obvious alternatives fall within the scope of the invention.
Claims (10)
1. A propylene carbonate-based electrolyte characterized in that: the solvent is a low-polarity chain solvent.
2. The propylene carbonate-based electrolyte according to claim 1, characterized in that: the diluent is one or more of trimethyl borate, triethyl borate, tripropyl borate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl butyl ether, ethyl butyl ether, propyl butyl ether, methyl ethyl ether and ethylene glycol dimethyl ether.
3. The propylene carbonate-based electrolyte according to claim 2, characterized in that: the volume ratio of the propylene carbonate solvent in the propylene carbonate-based electrolyte is 10-80%, and the volume ratio of the diluent in the propylene carbonate-based electrolyte is 20-90%.
4. The propylene carbonate-based electrolyte according to claim 3, characterized in that: in the propylene carbonate-based electrolyte, the concentration of the lithium salt is 0.5 to 5 mol/L.
5. The propylene carbonate-based electrolyte according to claim 4, wherein: the propylene carbonate-based electrolyte also includes a film forming additive.
6. The propylene carbonate-based electrolyte according to claim 5, wherein: the film forming additive is one or more than two of fluoroethylene carbonate, vinylene sulfate, lithium difluorophosphate and lithium bis (oxalato) borate, and the addition amount of the film forming additive is 0.1-10 wt% of the total mass of the propylene carbonate-based electrolyte.
7. The propylene carbonate-based electrolyte according to claim 6, wherein: the lithium salt is one or more than two of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bis (fluorosulfonyl) imide, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide and lithium bis (fluorooxalato) borate.
8. A lithium ion battery comprising the propylene carbonate based electrolyte of claims 1-7.
9. The lithium ion battery of claim 8, wherein: the lithium ion battery is a cylindrical lithium ion battery, a soft package lithium ion battery or an aluminum shell lithium ion battery.
10. The lithium ion battery of claim 8, wherein: the lithium ion battery is a lithium iron phosphate lithium ion battery, a lithium cobalt oxide lithium ion battery, a lithium manganate lithium ion battery, a nickel cobalt manganese ternary lithium ion battery or a nickel cobalt aluminum ternary lithium ion battery.
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| WO2023236007A1 (en) * | 2022-06-06 | 2023-12-14 | 宁德时代新能源科技股份有限公司 | Electrolytic solution, lithium secondary battery comprising same, battery module, battery pack, and electric apparatus |
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| CN105098248A (en) * | 2015-07-16 | 2015-11-25 | 湖南中大新能源科技有限公司 | Lithium ion battery electrolyte |
| CN105633464A (en) * | 2016-03-09 | 2016-06-01 | 华南师范大学 | Trimethyl borate additive contained high-voltage functional electrolyte and preparation method and application therefor |
| CN105655633A (en) * | 2016-03-30 | 2016-06-08 | 龙能科技（苏州）有限责任公司 | Lithium ion battery electrolyte suitable for lithium titanate battery |
| KR20180065755A (en) * | 2016-12-08 | 2018-06-18 | 주식회사 엘지화학 | non-aqueous liquid electrolyte and lithium secondary battery comprising the same |
| EP3637541A1 (en) * | 2017-06-08 | 2020-04-15 | National Institute for Materials Science | Non-aqueous electrolytic solution for lithium air batteries, and lithium air battery using same |
| CN110752408A (en) * | 2019-11-01 | 2020-02-04 | 珠海冠宇电池有限公司 | Electrolyte, preparation method thereof and lithium ion battery |
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| CN114583281A (en) * | 2022-03-25 | 2022-06-03 | 南开大学 | High-voltage-resistant ether-based electrolyte for low-temperature lithium metal battery |
| WO2023236007A1 (en) * | 2022-06-06 | 2023-12-14 | 宁德时代新能源科技股份有限公司 | Electrolytic solution, lithium secondary battery comprising same, battery module, battery pack, and electric apparatus |
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