CN111463485A - Lithium ion battery electrolyte and lithium ion battery - Google Patents
Lithium ion battery electrolyte and lithium ion battery Download PDFInfo
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- CN111463485A CN111463485A CN202010273635.4A CN202010273635A CN111463485A CN 111463485 A CN111463485 A CN 111463485A CN 202010273635 A CN202010273635 A CN 202010273635A CN 111463485 A CN111463485 A CN 111463485A
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- ion battery
- lithium ion
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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
- 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
- H01M10/05—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
- H01M10/42—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
Abstract
The invention discloses a lithium ion battery electrolyte, which comprises a non-aqueous organic solvent, lithium salt, an additive A, an additive B and an additive C. The invention also discloses a lithium ion battery comprising the anode, the diaphragm, the cathode and the lithium ion battery electrolyte. The electrolyte ensures that the battery has better cycle life, reduces the internal resistance of the battery in the use process, and avoids the potential safety hazard caused by the explosion-proof valve bouncing open when the battery is used at high temperature.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery electrolyte and a lithium ion battery.
Background
The existence of the cracks can promote the dissolution of transition metal elements in the ternary material, the electrolyte is oxidized by positive active substances, and meanwhile, the dissolved metal ions can be reduced and deposited on the surface of a negative electrode, and on the other hand, the transition metal ions can catalyze the decomposition of the electrolyte, so that the capacity attenuation, the internal resistance increase and the voltage attenuation of the ternary material in the circulating process are caused.
In view of the above, there is a need to develop an electrolyte compatible with a high-nickel high-voltage material system, so as to solve the problems of poor cycle performance, large internal resistance change during storage and charging/discharging of the battery, easy gas generation during high-temperature storage, and aggravated side reaction of the electrolyte under high voltage, which are common in the high-nickel material system battery.
Disclosure of Invention
The invention aims to provide a lithium ion battery electrolyte and a lithium ion battery which can be matched with a high-voltage high-nickel material system aiming at the defects of the prior art, so as to solve the problems of poor cycle performance, large internal resistance change of the battery in the storage and charging and discharging processes and easy gas generation in high-temperature storage of the high-voltage high-nickel material system battery at present.
In order to achieve the purpose, the invention adopts the technical scheme that: a lithium ion battery electrolyte comprising a non-aqueous organic solvent, a lithium salt and an additive a, an additive B and an additive C, wherein:
the additive A is at least one of lithium difluoro oxalate borate (L iDFOB), lithium bis (trifluoromethyl) sulfonyl imide (L iTFSI) and lithium bis (fluoro) sulfonyl imide (L iFSI);
the additive B is at least one of bis (2,2, 2-trifluoroethyl) carbonate (TFEC), Ethylene Sulfate (ES), Diphenyl Phosphorus Chloride (DPC), Fluorobenzene (FB), 1, 3-propylene sultone (PES), tripropyl phosphate (TPP), vinyl sulfate (DTD), Ethylene Propylene Carbonate (EPC) and chlorinated Polyethylene (PEC);
the additive C is at least one of fluoroethylene carbonate (FEMC), ethylene carbonate (VEC), Vinylene Carbonate (VC) and fluoroethylene carbonate (FEC).
Preferably, the mass percentage of the additive A in the lithium ion battery electrolyte is 0.5-3%.
Preferably, the mass percentage of the additive B in the lithium ion battery electrolyte is 0.5-5%.
Preferably, the mass percentage of the additive C in the lithium ion battery electrolyte is 0.5-15%.
Preferably, the non-aqueous organic solvent is a mixture of two or more of dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), Propylene Carbonate (PC), Ethylene Carbonate (EC), and Methyl Propyl Carbonate (MPC) mixed in an arbitrary ratio. The non-aqueous organic solvent is more preferably a mixture of any three of dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), and Ethylene Carbonate (EC) mixed in any ratio.
Preferably, the lithium salt is at least one of lithium hexafluorophosphate, lithium bis (oxalato) borate and lithium tetrafluoroborate
Preferably, the mass percentage of the lithium salt in the lithium ion battery electrolyte is 10-20%.
The invention also discloses a lithium ion battery which comprises an anode, a diaphragm, a cathode and the lithium ion battery electrolyte.
Compared with the prior art, the invention has the beneficial effects that:
the A, B, C three additives are added into the electrolyte, the additive A mainly has the effects of improving the cycle performance of the high-voltage high-nickel material battery, inhibiting the internal resistance of the battery from increasing in the high-temperature storage and cycle processes, improving the charge-discharge efficiency of the battery in the charge-discharge process and reducing self-discharge, and the additive also has positive influence on the high-temperature performance of the battery; the additive B is a low-impedance film-forming additive and mainly has the effects of forming a thin and compact SEI film on a graphite or silicon-carbon negative electrode interface, so that a high-nickel material is matched with a high-capacity high-compaction negative electrode material to have lower interface impedance, and lithium ions are favorably diffused; the additive C is a high-temperature-type improving additive, mainly plays a role in inhibiting the explosion-proof valve of the high-nickel battery from being bounced off due to excessive gas generation in the high-temperature long-term storage process, and has positive influence on the cycle life of the high-nickel battery. The invention ensures that the high-nickel ternary battery has better cycle life by optimizing the formula of the electrolyte, particularly the matching use of the three additives, reduces the internal resistance of the battery in the use process, and avoids the potential safety hazard caused by the explosion-proof valve bouncing off when the battery is used at high temperature.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are a part of embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The materials of the examples and comparative examples are commercially available, some of which are illustrated below:
VC: vinylene carbonate
L iDFOB lithium difluoro-oxalato-borate
TFEC: bis (2,2, 2-trifluoroethyl) carbonate
ES: sulfuric acid ethylene ester
FEC: fluoroethylene carbonate
DPC: diphenyl phosphorus chloride
FEMC: fluoromethyl ethyl carbonate
FB: fluorobenzene
PES: 1, 3-propylene sultone
VEC: ethylene carbonate
TPP: phosphoric acid tripropyl ester
L iFSI lithium bis (fluorosulfonyl) imide
DTD (time delay device): vinyl sulfate ester
EPC: ethylene propylene carbonate
PEC chlorinated polyethylene
FSI lithium bis (fluorosulfonyl) imide
L iTFSI lithium bis (trifluoromethylsulfonyl) imide
Example 1
Preparation of electrolyte solution in a glove box filled with argon (moisture < 10ppm, oxygen < 1ppm), Ethylene Carbonate (EC), dimethyl carbonate (DMC), and Ethyl Methyl Carbonate (EMC) were mixed uniformly at a mass ratio of 30:60:10 to obtain a mixed solvent, 10% of fluoroethylene carbonate VC, 1.0% of lithium difluorooxalato borate (L iDFOB), 1.0% of diphenylphosphoryl chloride (DPC) based on the total mass of the electrolyte solution were added to the mixed solvent, and 16% of lithium hexafluorophosphate (L iPF) based on the total mass of the electrolyte solution was slowly added6) And stirring until the electrolyte is completely dissolved to obtain the lithium ion battery electrolyte.
Examples 2 to 18
Examples 2 to 18 are also specific examples of the electrolyte preparation, and the parameters and preparation method are the same as those of example 1 except for the parameters shown in Table 1. The electrolyte formulation is shown in table 1.
Comparative examples 1 to 4
Comparative examples 1 to 4 the parameters and preparation method were the same as in example 1 except that the components of the electrolyte were added as shown in Table 1. The electrolyte formulation is shown in table 1.
TABLE 1 electrolyte compositions of examples 1-18 and comparative examples 1-4
Note: the concentration of the lithium salt is the mass percentage content in the electrolyte;
the contents of the components in the additive A, the additive B and the additive C are the mass percentage contents in the electrolyte;
the proportion of each component in the solvent is mass ratio.
And (3) performance testing:
fully stirring and uniformly mixing a positive active material of nickel-cobalt-aluminum manganese (NCA), lithium carbonate, a conductive agent of acetylene black and a binder of polyvinylidene fluoride (PVDF) in an N-methylpyrrolidone solvent system according to the mass ratio of 95: 1: 2, coating the mixture on an Al foil, drying and cold pressing to obtain a positive plate, wherein the compaction density of the positive plate is 3.45g/cm3。
Fully stirring and uniformly mixing the negative active material artificial graphite, the conductive agent acetylene black, the binder Styrene Butadiene Rubber (SBR) and the thickening agent sodium carboxymethyl cellulose (CMC) in a deionized water solvent system according to the mass ratio of 96: 2: 1, coating the mixture on a Cu foil, drying and cold pressing to obtain a negative plate, wherein the compaction density of the negative plate is 1.65g/cm3。
Polyethylene (PE) is used as a base film (12 μm) and a nano-alumina coating (2 μm) is coated on the base film to be used as a separation film.
And sequentially laminating the positive plate, the isolating membrane and the negative plate, winding the positive plate, the isolating membrane and the negative plate along the same direction to obtain a bare cell, then placing the bare cell in a steel shell, injecting the electrolyte prepared in the embodiments 1-18 and the comparative examples 1-4, and packaging to obtain the cylindrical lithium ion battery with the model number of 18650.
The batteries of examples 1 to 18 and comparative examples 1 to 4 were subjected to cycle performance test and high-temperature storage performance test, respectively, and the test results are shown in table 2. Wherein:
(1) cycle performance testing method
The battery is charged and discharged 500 times according to the standard (0.5C/1C), when the residual capacity of the battery is less than 70% of the rated capacity, the test is stopped, and the capacity, the platform capacity, the thickness and the weight of the battery are recorded. The calculation formula is as follows:
cycle capacity retention (%) of 0.5C/1C-500 cycles-discharge capacity/charge capacity 100%
(2) High-temperature storage performance testing method
The battery was fully charged as standard (0.5C/1C), then left at 60 + -2 deg.C for 2h, then discharged at 60 + -2 deg.C with a constant current of 1C to 3.0V, the remaining capacity was recorded, and finally left at 25 + -5 deg.C for 2h, and the appearance was observed. The calculation formula is as follows:
internal resistance change rate (%) (impedance after storage-impedance before storage)/impedance before storage) × 100%
Capacity retention (%) after storage/capacity before storage 100%
TABLE 2 test results of cycle performance and storage performance of batteries of examples 1 to 18 and comparative examples 1 to 4
The test results in table 2 show that the batteries of comparative examples 2 to 4, to which one or two of A, B and C additives are added independently, have the problems of poor cycle performance, poor high-temperature storage performance and large internal resistance change rate, and meanwhile, have the potential safety hazard that the explosion-proof valve is popped up at high temperature; the batteries of the embodiments 1 to 18 not only have effectively improved cycle performance, but also have smaller internal resistance change rate after high-temperature cycle and storage, and meanwhile, the explosion-proof valve is not popped up due to gas generation caused by storage, which shows that under the high-temperature condition, the effect of the A, B, C three additives used together is obviously better than that of the batteries used alone or the batteries used in a mixed manner, especially, the addition of the additive C can effectively inhibit the batteries from generating excessive gas in the high-temperature long-term storage process, prevent the explosion-proof valve of the batteries from being popped up, and have positive influence on the cycle life of the batteries; therefore, the electrolyte containing the additive A, B, C ensures that the battery has a better cycle life, reduces the internal resistance of the battery in the use process, and can avoid potential safety hazards caused by the explosion-proof valve bouncing off when the battery is used at high temperature.
Claims (9)
1. A lithium ion battery electrolyte comprising a non-aqueous organic solvent, a lithium salt and an additive A, an additive B and an additive C, wherein:
the additive A is at least one of lithium difluoro oxalate borate, lithium bis (trifluoromethyl) sulfonyl imide and lithium bis (fluoro) sulfonyl imide;
the additive B is at least one of bis (2,2, 2-trifluoroethyl) carbonate, ethylene sulfate, diphenyl phosphorus chloride, fluorobenzene, 1, 3-propylene sultone, tripropyl phosphate, ethylene sulfate, ethylene carbonate and chlorinated polyethylene;
the additive C is at least one of fluoroethylene carbonate, ethylene carbonate, vinylene carbonate and fluoroethylene carbonate.
2. The lithium ion battery electrolyte of claim 1, wherein the additive A is present in the lithium ion battery electrolyte in an amount of 0.5 to 3% by mass.
3. The lithium ion battery electrolyte of claim 1, wherein the additive B is present in the lithium ion battery electrolyte in an amount of 0.5 to 5% by mass.
4. The lithium ion battery electrolyte of claim 1, wherein the additive C is present in the lithium ion battery electrolyte in an amount of 0.5-15% by weight.
5. The lithium ion battery electrolyte of claim 1, wherein the non-aqueous organic solvent is a mixture of two or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, ethylene carbonate, and propyl methyl carbonate, mixed in any proportion.
6. The lithium ion battery electrolyte of claim 5, wherein the non-aqueous organic solvent is a mixture of any three of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and ethylene carbonate mixed in any proportion.
7. The lithium ion battery electrolyte of claim 1, wherein the lithium salt is at least one of lithium hexafluorophosphate, lithium bis (oxalato) borate, and lithium tetrafluoroborate.
8. The lithium ion battery electrolyte of claim 1, wherein the lithium salt is 10-20% by mass of the lithium ion battery electrolyte.
9. A lithium ion battery comprising a positive electrode, a separator, a negative electrode and the lithium ion battery electrolyte of any one of claims 1 to 8.
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Cited By (3)
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| CN113851728A (en) * | 2021-11-01 | 2021-12-28 | 上海如鲲新材料有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
| CN114204121A (en) * | 2021-11-01 | 2022-03-18 | 上海如鲲新材料股份有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
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Address after: 324012 No.62 Huayin North Road, Kecheng District, Quzhou City, Zhejiang Province Patentee after: New Asia Shanshan New Material Technology (Quzhou) Co.,Ltd. Address before: 324012 No.62 Huayin North Road, Kecheng District, Quzhou City, Zhejiang Province Patentee before: SHANSHAN ADVANCED MATERIALS (QUZHOU) Co.,Ltd. |
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