CN112448033A - High-voltage lithium ion battery electrolyte and long-cycle-life high-voltage lithium ion battery - Google Patents
High-voltage lithium ion battery electrolyte and long-cycle-life high-voltage lithium ion battery Download PDFInfo
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- CN112448033A CN112448033A CN201910836633.9A CN201910836633A CN112448033A CN 112448033 A CN112448033 A CN 112448033A CN 201910836633 A CN201910836633 A CN 201910836633A CN 112448033 A CN112448033 A CN 112448033A
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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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- 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
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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
- H01M10/42—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
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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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
Abstract
The invention belongs to the technical field of batteries, and discloses a high-voltage lithium ion battery electrolyte and a high-voltage lithium ion battery with long cycle life. The electrolyte of the high-voltage lithium ion battery comprises a non-aqueous organic solvent, an electrolyte and a film forming additive, wherein the film forming additive contains a negative film forming additive and has a structure of
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a high-voltage lithium ion battery electrolyte and a high-voltage lithium ion battery with long cycle life.
Background
The lithium ion battery has the advantages of high energy density, long cycle life, no memory effect and the like, and is widely researched and applied. At present, the application of lithium ion batteries in the fields of power automobiles and hybrid automobiles puts higher requirements on the energy density of the lithium ion batteries. Currently, the anode materials of commercial high-capacity lithium ion batteries mainly include lithium cobaltate, lithium manganate, lithium nickel manganese, ternary materials and the like, wherein increasing the cut-off voltage of the batteries is considered to be an effective method for increasing the energy density. However, at high voltage the crystal structure is destroyed and the transition metal ions are separated from the crystal lattice into the solvent system, and the unique solvation structure can cause serious damage to the carbonate solvent and hexafluorophosphate, thereby causing serious loss of battery capacity and even 'cycle skipping'. Therefore, the development of high voltage lithium ion batteries requires more stable high voltage electrolytes to prevent severe solvolysis reactions.
Disclosure of Invention
The invention aims to overcome the defects of the background technology and provide a high-voltage lithium ion battery electrolyte, which effectively solves the problems of capacity attenuation and poor cycle performance of a high-voltage lithium ion secondary battery.
In order to achieve the purpose of the invention, the high-voltage lithium ion battery electrolyte comprises a non-aqueous organic solvent, an electrolyte and a film forming additive, wherein the film forming additive contains a negative film forming additive and a phosphorus-containing ester additive shown in a structural formula 1:
in the formula 1, R1、R2、R3Each independently selected from a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an aralkyl group having 6 to 10 carbon atoms, an oxyalkyl group, a silyl group, a carbonyl group, a carboxyl group, a carbonate group, a fluorooxyalkyl group, a fluorosilyl group, a fluoroaralkyl group, and R is1、R2、R3Contains at least one fluorine atom.
Preferably, the alkyl group having 1 to 10 carbon atoms is a methyl group, an ethyl group, a propyl group, or a cyclohexyl group; the aralkyl with 6-10 carbon atoms is phenyl, tolyl, xylyl, phenethyl and cyclohexylphenyl.
More preferably, the phosphorus-containing ester additive shown in the structural formula 1 is one or more of compounds 1 to 8:
further preferably, the mass percentage of the phosphorus-containing ester additive shown in the structural formula 1 in the electrolyte solution of the battery is 0.5% -4%, for example 0.8% -1.2%.
Further, the negative electrode film forming additive is selected from Vinylene Carbonate (VC), vinyl sulfate (DTD), 1, 3-Propane Sultone (PS), fluoroethylene carbonate (FEC), lithium difluorophosphate (LiDFP), lithium difluorooxalate phosphate (liddrop), lithium tetrafluoroborate (LiBF)4) Lithium difluorooxalato borate (LiDFOB), ethylene carbonate (VEC), Succinonitrile (SN), Adiponitrile (ADN), ethylene glycol bis (propionitrile) ether (DENE), triphenyl phosphite.
Preferably, the negative electrode film forming additive is vinylene carbonate, 1, 3-propane sultone and succinonitrile, or vinylene carbonate and succinonitrile, or vinyl sulfate and succinonitrile, or lithium difluorophosphate and succinonitrile, or fluoroethylene carbonate and succinonitrile.
Further, the non-aqueous organic solvent is selected from cyclic carbonates, chain carbonates, carboxylic esters, fluoro carbonates, fluoro carboxylic esters, fluoro ethers and sulfone solvents; wherein the cyclic carbonate solvent is one or more of ethylene carbonate, propylene carbonate and butylene carbonate, and the mass percent of the cyclic carbonate solvent in the non-aqueous organic solvent is 5-40%; the chain carbonate solvent is one or more of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, dipropyl carbonate and methyl propyl carbonate, and the mass percentage of the chain carbonate solvent in the non-aqueous organic solvent is 5-40%; the carboxylic ester solvent is one or more of ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, ethyl propionate, propyl propionate and ethyl n-butyrate, and the mass percentage of the carboxylic ester solvent in the non-aqueous organic solvent is 5-40%; the fluorinated carbonate solvent is one or more of fluorinated ethylene carbonate, difluoroethylene carbonate, dimethyl fluorocarbonate, fluoroethyl carbonate, diethyl fluorocarbonate, diethyl difluorocarbonate and propylene fluorocarbonate, and the mass percentage of the fluorinated carbonate solvent in the non-aqueous organic solvent is 5-40%; the fluorinated carboxylic ester solvent is one or more of ethyl fluoroformate, ethyl fluoroacetate, propyl fluoroformate, propyl fluoropropionate, butyl fluoroformate and butyl fluoroacetate, and the mass percentage of the fluorinated carboxylic ester solvent in the non-aqueous organic solvent is 5-40%; the fluoroether solvent is one or more of 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether and 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, and the mass percentage of the fluoroether solvent in the non-aqueous organic solvent is 5-40%.
In the present invention, the electrolyte is not limited as long as it is used as an electrolyte in a target nonaqueous electrolyte secondary battery, and a known electrolyte can be used arbitrarily. In the case where the nonaqueous electrolytic solution of the present invention is used for a lithium secondary battery, a lithium salt is generally used as an electrolyte, and among them, lithium hexafluorophosphate, lithium difluorophosphate, lithium tetrafluorophosphate, lithium difluorooxalato phosphate, lithium tetrafluoroborate, lithium bisoxalato borate, lithium difluorooxalato borate, lithium bisfluorosulfonylimide, and lithium bistrifluoromethanesulfonylimide are preferable as an electrolyte in the present invention, and lithium hexafluorophosphate is more preferable.
Furthermore, the electrolyte is preferably 10-15% by mass in the non-aqueous electrolyte solution.
On the other hand, the invention also provides a high-voltage lithium ion battery with long cycle life, which comprises a positive electrode, a negative electrode, a diaphragm and the high-voltage lithium ion battery electrolyte.
Further, the active material of the positive electrode is LiNi1-x-yCoxMnyAlzOne or more of lithium cobaltate, lithium manganate, lithium nickel manganese oxide and manganese-rich solid solution, wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and x + y + z is more than or equal to 0 and less than or equal to 1; the negative electrode material is one or more of natural graphite, artificial graphite, lithium titanate, a silicon-carbon negative electrode and a silicon negative electrode.
Further, the upper limit cut-off voltage of the lithium ion battery is 4.2-5V.
In the electrolyte, the HOMO energy of the phosphorus-containing ester additive shown in the structural formula 1 is higher than that of ethylene carbonate, and oxidation reaction preferentially occurs on the surface of a ternary material to form a stable and compact CEI film, so that the oxidation reaction of the electrolyte on the surface of an electrode is reduced; meanwhile, an interface film with low impedance is formed on the surface of the negative electrode, so that the dynamic characteristics in the battery are improved, and the cycle life of the battery is prolonged. In addition, other film forming additives in the invention can broaden the electrochemical window, or the ethylene sulfate and the like are preferentially reduced and decomposed on the surface of the negative electrode to form an excellent solid electrolyte film, enrich the chemical composition of the SEI film, adjust the impedance, and improve the high-low temperature performance, the rate capability and the storage performance of the battery.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention. It is to be understood that the following description is only illustrative of the present invention and is not to be construed as limiting the present invention.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular. Further, the technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
Example 1
Preparing an electrolyte:
in a glove box filled with argon (the oxygen content is less than or equal to 1ppm, the water content is less than or equal to 1ppm), ethylene carbonate EC, propylene carbonate PC, diethylene carbonate DEC, propyl propionate PP and fluoroethylene carbonate FEC are uniformly mixed in a volume ratio of 25:10:20:40:5 and are continuously stirred, and 12.5 percent of LiPF is added into the mixed solution6. Then, compound 1, which accounts for 1% of the mass of the battery electrolyte solution, vinylene carbonate VC, which accounts for 1% of the mass of the battery electrolyte solution, 1, 3-propane sultone PS, which accounts for 1% of the mass of the battery electrolyte solution, and succinonitrile SN, which accounts for 1% of the mass of the battery electrolyte solution, were added to the mixed solution, and stirred to be completely dissolved, thereby obtaining the electrolyte solution of example 1.
Preparing a lithium ion battery:
LiNi as positive electrode active material0.5Co0.3Mn0.2O2The conductive agent acetylene black and the binder polyvinylidene fluoride are fully stirred and uniformly mixed in an N-methyl pyrrolidone system according to the mass ratio of 95:3:2, and then coated on an aluminum foil to be dried and cold-pressed, so that the positive plate is obtained.
Fully stirring and uniformly mixing a negative electrode active substance Si (15%)/AG (85%), a conductive agent super carbon black, a thickening agent carboxymethylcellulose sodium and a binder styrene butadiene rubber in a deionized water solvent system according to a mass ratio of 95:1:2:2, coating the mixture on a copper foil, drying and cold-pressing to obtain the negative electrode plate.
Polyethylene is used as a base film, and a nano aluminum oxide coating is coated on the base film to be used as a diaphragm.
And stacking the positive plate, the powder and the negative plate in sequence to enable the diaphragm to be positioned between the positive plate and the negative plate to play an isolation role, and winding to obtain the bare cell. And placing the bare cell in an outer package, injecting the prepared electrolyte, and carrying out processes of packaging and placing, formation, aging, secondary packaging, capacity grading and the like to obtain the ternary silicon-carbon lithium ion battery.
Examples 2 to 12
Examples 2 to 12 were the same as example 1 except that the electrolyte solvent and the additive composition and content were added as shown in Table 1.
Table 1 battery electrolyte compositions of examples 1-12
Comparative examples 1 to 8
Comparative examples 1 to 8 were the same as example 1 except that the electrolyte solvent, the additive composition and the content were added as shown in Table 2.
TABLE 2 electrolyte compositions for batteries of comparative examples 1-8
Effects of the embodiment
(1) Test of ordinary temperature cycle Performance
At 25 ℃, the formed lithium ion battery is charged to 4.35V according to a constant current and a constant voltage of 1C, the current is cut off to 0.02C, and then the lithium ion battery is discharged to 3.0V according to a constant current of 1C. The 850 th cycle capacity retention rate was calculated after 850 cycles of charge/discharge. The calculation formula is as follows:
capacity retention rate at 850 th week (850 th cycle discharge capacity/first cycle discharge capacity × 100%)
(2) High temperature cycle performance test at 45 DEG C
And (3) placing the formed lithium ion battery in an environment of 45 ℃ to be charged to 4.35V according to a constant current and a constant voltage of 1C, stopping the current to be 0.02C, and then discharging to 3.0V according to a constant current of 1C. The capacity retention rate was calculated at 300 cycles after 300 cycles of charge/discharge. The calculation formula is as follows:
capacity retention at 300 th week (%) - (300 th week cycle discharge capacity/first week cycle discharge capacity x 100%)
(3) Low temperature discharge performance test at-20 deg.C
And charging the formed lithium ion battery to 4.35V at constant current and constant voltage according to 1C, stopping current to 0.02C, then discharging to 3.0V at constant current according to 1C, and recording the normal-temperature discharge capacity. The cell charged to 4.35V with 1C constant current and constant voltage was left to stand at-20 deg.C for 4h, and then discharged to 2.5V with 0.5C constant current. The discharge capacity ratio at-20 ℃ was calculated. The calculation formula is as follows:
the discharge capacity at-20 ℃ in proportion (%) of-20 ℃ discharge capacity/discharge capacity at room temperature is 100%
The test results of the lithium ion batteries of the respective examples and comparative examples are shown in table 3.
TABLE 3 results of cell performance test of examples 1-12 and comparative examples 1-8
In tables 1 to 3, the letter abbreviations of the chemical substances have the following corresponding names:
EC (ethylene carbonate), PC (1,3 propane sultone), DEC (diethylene carbonate), PP (propyl propionate), EP (ethyl propionate), FEC (fluoroethylene carbonate), FEMC (fluoroethylene carbonate), D2(1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether), VC (vinylene carbonate), DTD (vinyl sulfate), LiDFP (lithium difluorophosphate), SN (succinonitrile).
As can be seen from examples 1 to 8 and comparative examples 1 to 4, for LiNi1-x-y CoxMnyAlzThe normal-temperature and low-temperature cycle performance of the lithium ion battery adopting the electrolyte in the embodiment 1-8 is obviously superior to that of the lithium ion battery in the comparative example 1-4 in a silicon-carbon system. The interfacial film formed by the boundary of the phosphorus-containing ester additive shown in the structural formula 1 is an excellent solid electrolyte interfacial film and plays a role in adjusting impedance and improving cycle performance.
Compared with examples 9-12, comparative example 5 has poor high temperature cycle performance despite the addition of a certain amount of the phosphorus-containing ester additive represented by formula 1, and the reason for this is analyzed that comparative example 5 lacks film-forming additives such as VC, DTD, LiDFP, FEC, SN, etc., and cannot form a high temperature resistant SEI film, resulting in gas generation or capacity loss. Comparative example 6 does not contain any additive, and a uniform and stable low-resistance SEI film cannot be formed on the surface of the electrode material, and the carbonate solvent is rapidly decomposed at high voltage, so that the cycle life and the performance performances at high and low temperatures are poor.
Compared with the example 1, 5% and 0.02% of the phosphorus-containing ester additive shown in the structural formula 1 are respectively added in the comparative example 7 and the comparative example 8, but the capacity retention rate and the low-temperature discharge efficiency of the lithium ion battery subjected to normal-temperature cycle for 1000 weeks are relatively low, which shows that the impedance is increased by adding too much of the phosphorus-containing ester additive, and the effect is not obvious by adding too little of the phosphorus-containing ester additive, so that the addition amount of the phosphorus-containing ester additive shown in the structural formula 1 needs to be controlled within a proper concentration range to obtain the.
In conclusion, the electrolyte can ensure high-voltage LiNi through the combined action of the phosphorus-containing ester additive shown in the structural formula 1 and other negative electrode film-forming additives on the electrode/electrolyte interface0.5Co0.3Mn0.2O2SiliconThe carbon lithium ion battery obtains long cycle life and excellent high and low temperature discharge performance.
It will be understood by those skilled in the art that the foregoing is merely exemplary of the present invention, and is not intended to limit the invention to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The high-voltage lithium ion battery electrolyte is characterized by comprising a non-aqueous organic solvent, an electrolyte and a film forming additive, wherein the film forming additive contains a negative electrode film forming additive and a phosphorus-containing ester additive shown in a structural formula 1:
in the formula 1, R1、R2、R3Each independently selected from a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an aralkyl group having 6 to 10 carbon atoms, an oxyalkyl group, a silyl group, a carbonyl group, a carboxyl group, a carbonate group, a fluorooxyalkyl group, a fluorosilyl group, a fluoroaralkyl group, and R is1、R2、R3Contains at least one fluorine atom.
2. The high-voltage lithium ion battery electrolyte according to claim 1, wherein the alkyl group having 1 to 10 carbon atoms is a methyl group, an ethyl group, a propyl group, or a cyclohexyl group; the aralkyl with 6-10 carbon atoms is phenyl, tolyl, xylyl, phenethyl and cyclohexylphenyl.
3. The high voltage lithium ion battery electrolyte of claim 1, wherein the phosphorus-containing ester additive represented by formula 1 is one or more of compounds 1-8:
preferably, the mass percentage of the phosphorus-containing ester additive shown in the structural formula 1 in the electrolyte solution of the battery is 0.5% -4%, for example 0.8% -1.2%.
4. The high voltage lithium ion battery electrolyte of claim 1 wherein the negative electrode film-forming additive is selected from at least two of vinylene carbonate, vinyl sulfate, 1, 3-propane sultone, fluoroethylene carbonate, lithium difluorophosphate, lithium difluorooxalate phosphate, lithium tetrafluoroborate, lithium difluorooxalate borate, vinylethylene carbonate, succinonitrile, adiponitrile, ethylene glycol bis (propionitrile) ether, triphenyl phosphite.
5. The high voltage lithium ion battery electrolyte of claim 1 wherein the negative electrode film forming additive is vinylene carbonate, 1, 3-propane sultone and succinonitrile, or vinylene carbonate and succinonitrile, or vinyl sulfate and succinonitrile, or lithium difluorophosphate and succinonitrile, or fluoroethylene carbonate and succinonitrile.
6. The high voltage lithium ion battery electrolyte of claim 1 wherein the non-aqueous organic solvent is selected from the group consisting of cyclic carbonates, chain carbonates, carboxylates, fluorocarbonates, fluorocarboxylates, fluoroethers, and sulfone-based solvents; wherein the cyclic carbonate solvent is one or more of ethylene carbonate, propylene carbonate and butylene carbonate, and the mass percent of the cyclic carbonate solvent in the non-aqueous organic solvent is 5-40%; the chain carbonate solvent is one or more of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, dipropyl carbonate and methyl propyl carbonate, and the mass percentage of the chain carbonate solvent in the non-aqueous organic solvent is 5-40%; the carboxylic ester solvent is one or more of ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, ethyl propionate, propyl propionate and ethyl n-butyrate, and the mass percentage of the carboxylic ester solvent in the non-aqueous organic solvent is 5-40%; the fluorinated carbonate solvent is one or more of fluorinated ethylene carbonate, difluoroethylene carbonate, dimethyl fluorocarbonate, fluoroethyl carbonate, diethyl fluorocarbonate, diethyl difluorocarbonate and propylene fluorocarbonate, and the mass percentage of the fluorinated carbonate solvent in the non-aqueous organic solvent is 5-40%; the fluorinated carboxylic ester solvent is one or more of ethyl fluoroformate, ethyl fluoroacetate, propyl fluoroformate, propyl fluoropropionate, butyl fluoroformate and butyl fluoroacetate, and the mass percentage of the fluorinated carboxylic ester solvent in the non-aqueous organic solvent is 5-40%; the fluoroether solvent is one or more of 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether and 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, and the mass percentage of the fluoroether solvent in the non-aqueous organic solvent is 5-40%.
7. The high voltage lithium ion battery electrolyte of claim 1, wherein the electrolyte is one or more of lithium hexafluorophosphate, lithium difluorophosphate, lithium tetrafluorophosphate, lithium difluorooxalato phosphate, lithium tetrafluoroborate, lithium bis oxalato borate, lithium difluorooxalato borate, lithium bis fluorosulfonylimide, lithium bis trifluoromethanesulfonylimide, preferably lithium hexafluorophosphate; preferably, the mass percentage of the electrolyte in the non-aqueous electrolyte solution is 10-15%.
8. A long cycle life high voltage lithium ion battery comprising a positive electrode, a negative electrode, a separator and the high voltage lithium ion battery electrolyte of any of claims 1-7.
9. The long-cycle-life high-voltage lithium ion battery according to claim 8, wherein the active material of the positive electrode is LiNi1-x-yCoxMnyAlzOne or more of lithium cobaltate, lithium manganate, lithium nickel manganese oxide and manganese-rich solid solution, wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and x + y + z is more than or equal to 0 and less than or equal to 1; the negative electrode material is one or more of natural graphite, artificial graphite, lithium titanate, a silicon-carbon negative electrode and a silicon negative electrode.
10. The long-cycle-life high-voltage lithium-ion battery according to claim 8, wherein the lithium-ion battery has an upper cutoff voltage of 4.2-5V.
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| CN113809398A (en) * | 2021-08-12 | 2021-12-17 | 东莞市创明电池技术有限公司 | Electrolyte additive, electrolyte and sodium secondary battery |
| CN115763960A (en) * | 2022-12-05 | 2023-03-07 | 惠州亿纬锂能股份有限公司 | Silicon-based negative electrode electrolyte, preparation method and lithium ion battery thereof |
| CN115799643A (en) * | 2023-01-18 | 2023-03-14 | 如鲲(江苏)新材料科技有限公司 | Nonaqueous electrolyte solution, lithium ion battery, battery module, battery pack, and electric device |
| CN116247300A (en) * | 2023-05-09 | 2023-06-09 | 蓝固(湖州)新能源科技有限公司 | High-voltage electrolyte additive, electrolyte and lithium ion battery |
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| CN115799643A (en) * | 2023-01-18 | 2023-03-14 | 如鲲(江苏)新材料科技有限公司 | Nonaqueous electrolyte solution, lithium ion battery, battery module, battery pack, and electric device |
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