CN112563572A - High-nickel lithium ion battery electrolyte used under high voltage and lithium ion battery - Google Patents
High-nickel lithium ion battery electrolyte used under high voltage and lithium ion battery Download PDFInfo
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- CN112563572A CN112563572A CN201910918915.3A CN201910918915A CN112563572A CN 112563572 A CN112563572 A CN 112563572A CN 201910918915 A CN201910918915 A CN 201910918915A CN 112563572 A CN112563572 A CN 112563572A
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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
- 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
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- 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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Abstract
The invention belongs to the technical field of batteries, and discloses a high-nickel lithium ion battery electrolyte used under high voltage and a lithium ion battery. The high-nickel lithium ion battery electrolyte used under high voltage comprises a non-aqueous organic solvent, an electrolyte, a first additive shown in a structural formula 1, a second additive containing a lithium salt and a third additive containing a thioester. In the electrolyte, the first additive shown in the structural formula 1 stabilizes an electrode and an electrolyte interface through chelation with transition metal ions, protects a positive electrode material, and reduces side reactions of a positive electrode and the electrolyte, so as to achieve the purpose of improving high-temperature performance. The second type of lithium salt additive containing phosphorus can form a stable SEI film on the surface of the negative electrode, reduce interface impedance and polarization reaction, and improve the cycle performance and the coulombic efficiency of the battery. The third film forming additive can form an SEI film mainly containing sulfur-containing inorganic matters, improve the high temperature resistance of the SEI film and inhibit gas generation.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a high-nickel lithium ion battery electrolyte used under high voltage and a lithium ion battery.
Background
In recent years, with the increase in performance of electronic devices and the application of lithium ion batteries to vehicle-mounted power sources for driving and large-sized power sources for stationary use, the overall performance of secondary batteries used in the battery field has been increasingly required, and it has been required to achieve high performance of secondary battery characteristics at a high level, for example, an increase in capacity, high-temperature storage characteristics, cycle characteristics, and the like. In addition, the development trend of vehicle-mounted power supplies and large-scale power supplies for fixing is also the trend of improving the energy density of lithium ions, and the development of the high-voltage ternary cathode material is an effective way for improving the energy density of the lithium ions, but with the increase of the nickel content in the cathode material, the gram capacity is increased, and the defects of unstable structure, over-quick increase of impedance in the circulation process, quick attenuation of the capacity, easy gas generation in high-temperature storage and the like are brought along, and even safety accidents occur in serious cases.
Disclosure of Invention
The invention aims to overcome the defects of the background technology and provide a high-nickel lithium ion battery electrolyte used under high voltage aiming at the requirements of the prior art.
In order to achieve the purpose of the invention, the electrolyte of the high-nickel lithium ion battery used under high voltage comprises a non-aqueous organic solvent, an electrolyte, a first additive shown in a structural formula 1, a second additive containing lithium phosphate and a third additive containing thioesters:
wherein R is1Selected from alkyl with 1-10 carbon atoms and alkenyl with 2-10 carbon atoms, R2、R3、R4Each independently selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms and an aralkyl group having 6 to 10 carbon atoms.
According to some embodiments of the invention, the first type of additive represented by structural formula 1 is one or more of compounds 1-10:
preferably, the mass percentage of the first additive shown in the structural formula 1 in the electrolyte is 0.1-5%.
Further, the second type of lithium phosphate-containing additive is selected from one or more of lithium difluorophosphate, lithium tetrafluorophosphate, lithium trioxalate phosphate, lithium difluorobis-oxalate phosphate, and lithium tetrafluorooxalate phosphate.
Preferably, the mass percentage of the second phosphorus-containing lithium salt additive in the electrolyte is 0.01-5%.
Further, the third type of sulfur-containing ester additive is one or more selected from vinyl sulfate, propylene sulfate, propane sultone, butane sultone, propylene sultone, butene sultone and vinyl methane disulfonate.
Preferably, the third sulfur-containing ester additive accounts for 0.2-5% of the electrolyte by mass.
Further, the non-aqueous organic solvent is selected from one or more of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, propyl ethyl carbonate, ethyl acetate, ethyl propionate, ethyl butyrate, propyl acetate, propyl propionate, butyl butyrate, fluoroethylene carbonate, difluoroethylene carbonate, ethyl fluorocarbonate, ethyl fluoroacetate, propyl fluorocarboxylate, propyl fluoropropionate, butyl fluorocarboxylate, butyl fluoroacetate, dimethyl sulfone, sulfolane, 1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, and 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether.
Preferably, the mass percentage of the nonaqueous organic solvent in the electrolyte is 50-90%.
The electrolyte solution of the present invention is not limited to the above-mentioned electrolyte, and any known electrolyte may be used as long as it is used as an electrolyte in the electrolyte solution of the present invention. 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, one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium difluorophosphate, lithium bisoxalato borate, lithium difluorooxalato borate, lithium tetrafluorooxalato phosphate, lithium difluorooxalato phosphate, lithium bisfluorosulfonylimide, lithium bistrifluorosulfonylmethylimide, and lithium fluorosulfonyl (trifluoromethanesulfonylmethyl) imide are preferable, and among them, lithium hexafluorophosphate is more preferable.
Further, the mass percentage of the electrolyte in the electrolyte is 0.1-20%.
On the other hand, the invention also provides a high-nickel lithium ion battery used under high voltage, which comprises a positive electrode, a negative electrode, a diaphragm and a non-aqueous electrolyte solution, wherein the electrolyte is the high-nickel lithium ion battery electrolyte used under high voltage.
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 4.35-5V.
In the electrolyte, the first additive shown in the structural formula 1 stabilizes an electrode and an electrolyte interface through chelation with transition metal ions, protects a positive electrode material, and reduces side reactions of a positive electrode and the electrolyte, so as to achieve the purpose of improving high-temperature performance. The second type of lithium salt additive containing phosphorus can form a stable SEI film on the surface of the negative electrode, reduce interface impedance and polarization reaction, and improve the cycle performance and the coulombic efficiency of the battery. The third film forming additive can form an SEI film mainly containing sulfur-containing inorganic matters, improve the high temperature resistance of the SEI film and inhibit gas generation.
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
In a glove box filled with argon and having oxygen content less than or equal to 1ppm and water content less than or equal to 1ppm, ethylene carbonate, propylene carbonate, fluoroethylene carbonate and ethyl acetate are mixed according to the mass ratio of 20:10:5:65Uniformly mixing, and adding compound 1 accounting for 1% of the electrolyte, lithium difluorophosphate accounting for 1% of the electrolyte and propane sulfonic acid lactone accounting for 1% of the electrolyte into the mixed solution. Then adding LiPF accounting for 12.5 percent of the mass of the electrolyte into the mixed solution6The solution was completely dissolved by stirring to obtain an electrolyte solution of example 1.
The prepared electrolyte solution is injected into the electrolyte prepared by LiNi0.6Co0.2Mn0.2O2And (3) as a positive electrode material, Si (15%)/AG (85%) is used as a negative electrode in the lithium ion battery cell, and after liquid injection is finished, the processes of packaging, standing, formation, aging, secondary packaging, capacity grading and the like are carried out to obtain the high-capacity lithium ion battery.
Examples 2 to 14
Examples 2 to 14 were the same as example 1 except that the electrolyte solvent, lithium salt, and additive composition and content were added as shown in table 1, and are specifically shown in table 1.
TABLE 1 electrolyte compositions of examples 1-14
Comparative examples 1 to 6
Comparative examples 1 to 6 were the same as example 1 except that the electrolyte solvent, lithium salt, and additive composition and content were added as shown in table 1, as shown in table 2.
TABLE 2 electrolyte compositions of comparative examples 1-6
Effects of the embodiment
(1) And (3) testing the normal-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 capacity retention rate was calculated at 300 cycles after 300 cycles of charge/discharge. The calculation formula is as follows:
the capacity retention rate at 300 th week was 300 th cycle discharge capacity/first cycle discharge capacity × 100%.
(2) High temperature storage performance at 60 ℃: the cell was charged and discharged once at room temperature at 0.5C, the current was cut off at 0.02C and the initial capacity was recorded. Fully filling the battery at a constant current and a constant voltage of 0.5C, and testing the initial thickness of the battery; storing the fully charged battery in a constant temperature environment of 60 ℃ for 14 days, testing the thermal thickness of the battery, and calculating thermal state expansion; after the battery is cooled to the normal temperature for 6 hours, testing the cold thickness, the voltage and the internal resistance, discharging to 3.0V at 0.5C, and recording the residual capacity of the battery; and then, the charging and discharging are carried out for 3 times according to 0.5C, the maximum capacity in the 3 times of cycles, namely the recovery capacity of the battery, is recorded, and the residual rate of the battery capacity and the recovery rate of the battery capacity are calculated. The calculation formula is as follows:
the thermal state expansion ratio (%) of the battery is (thermal thickness-initial thickness)/initial thickness × 100%;
battery capacity remaining rate (%) — remaining capacity/initial capacity × 100%;
the battery capacity recovery ratio (%) — recovery capacity/initial capacity × 100%.
Table 3 shows the results of the cell performance tests of examples 1 to 14 and comparative examples 1 to 6:
TABLE 3 Battery Performance test results
In the above tables 1-2, the letters of each chemical substance are abbreviated as follows:
EC (ethylene carbonate), PC (propylene carbonate), DEC (diethylene carbonate), EA (ethyl acetate), PP (propyl propionate), FEC (fluoroethylene carbonate), LiPF6(lithium hexafluorophosphate), PS (propane sultone), DTD (vinyl sulfate), BS (butenesulfonic acid lactone)Esters), PST (propylene sulfonic acid lactone), MMDS (vinyl methane disulfonate), LiDFP (lithium difluorophosphate), IPTS (isocyanatopropyltriethoxysilane).
As can be seen from examples 1 to 14 and comparative examples 1 to 4, the battery containing the first additive, the second additive and the third additive, which are shown in the structural formula 1, has a higher retention rate of 25 ℃ cyclic capacity and a lower thermal state expansion rate after 14 days of high-temperature storage at 60 ℃ than that of different lithium ion batteries containing only one or two of the first additive, the second additive and the third additive, which indicates that the electrolyte can ensure that the high-nickel battery can obtain long cyclic performance and excellent high-temperature storage performance under high voltage through the synergistic effect of the first additive, the second additive and the third additive, which are shown in the structural formula 1.
Comparative examples 5 to 6 were added with three additives simultaneously, but the room temperature cycle capacity retention rate and the high temperature storage capacity residual rate were significantly different from examples 1 to 14, which indicates that the first type of additive shown in formula 1 was added too little to protect the positive electrode, and was unable to inhibit ballooning caused by decomposition of the electrolyte, and too much addition resulted in too much impedance and poor cycle performance, i.e., the first type of additive shown in formula 1 was required to be controlled within a suitable dosage range to obtain superior battery 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 electrolyte of the high-nickel lithium ion battery used under high voltage is characterized by comprising a non-aqueous organic solvent, an electrolyte, a first additive shown in a structural formula 1, a second additive containing lithium phosphate and a third additive containing thioesters, wherein the first additive is a mixture of the following components:
wherein R is1Selected from alkyl with 1-10 carbon atoms and alkenyl with 2-10 carbon atoms, R2、R3、R4Each independently selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms and an aralkyl group having 6 to 10 carbon atoms.
2. The high-nickel lithium ion battery electrolyte for use at high voltage according to claim 1, wherein the first type of additive represented by structural formula 1 is one or more of compounds 1-10:
preferably, the mass percentage of the first additive shown in the structural formula 1 in the electrolyte is 0.1-5%.
3. The high-nickel lithium ion battery electrolyte for use at high voltages of claim 1, wherein the second type of lithium phosphate-containing additive is selected from one or more of lithium difluorophosphate, lithium tetrafluorophosphate, lithium trioxalate phosphate, lithium difluorobis-oxalate phosphate, lithium tetrafluorooxalate phosphate; preferably, the mass percentage of the second phosphorus-containing lithium salt additive in the electrolyte is 0.01-5%.
4. The high-nickel lithium ion battery electrolyte for use at high voltages of claim 1, wherein the third type of sulfur-containing ester additive is selected from one or more of vinyl sulfate, propylene sulfate, propane sultone, butane sultone, propylene sultone, butene sultone, and vinyl methane disulfonate; preferably, the third sulfur-containing ester additive accounts for 0.2-5% of the electrolyte by mass.
5. The high nickel lithium ion battery electrolyte for use at high voltages of claim 1, the non-aqueous organic solvent is selected from one or more of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, propyl ethyl carbonate, ethyl acetate, ethyl propionate, ethyl butyrate, propyl acetate, propyl propionate, butyl butyrate, fluoroethylene carbonate, difluoroethylene carbonate, ethyl fluoro-formate, ethyl fluoro-acetate, propyl fluoro-formate, propyl fluoro-propionate, butyl fluoro-formate, butyl fluoro-acetate, dimethyl sulfone, sulfolane, 1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, 1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether.
6. The electrolyte for the high-nickel lithium ion battery used under high voltage according to claim 5, wherein the mass percentage of the non-aqueous organic solvent in the electrolyte is 50-90%.
7. The high nickel lithium ion battery electrolyte for use at high voltages of claim 1, wherein the electrolyte is one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium difluorophosphate, lithium bis (oxalato) borate, lithium difluorooxalato borate, lithium tetrafluorooxalato phosphate, lithium difluorooxalato phosphate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, lithium fluorosulfonyl (trifluoromethanesulfonyl methyl) imide.
8. The electrolyte for the high-nickel lithium ion battery used under high voltage according to claim 7, wherein the mass percentage of the electrolyte in the electrolyte is 0.1-20%.
9. A high-nickel lithium ion battery used under high voltage, which comprises a positive electrode, a negative electrode, a separator and a non-aqueous electrolyte solution, wherein the electrolyte solution is the high-nickel lithium ion battery electrolyte solution used under high voltage according to any one of claims 1 to 8.
10. The high-nickel lithium ion battery for use at high voltage according to claim 9, 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; preferably, the upper cut-off voltage of the lithium ion battery is 4.35-5V.
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Address after: No.62 Huayin North Road, Kecheng District, Quzhou City, Zhejiang Province Patentee after: New Asia Shanshan New Material Technology (Quzhou) Co.,Ltd. Address before: No.62 Huayin North Road, Kecheng District, Quzhou City, Zhejiang Province Patentee before: SHANSHAN ADVANCED MATERIALS (QUZHOU) Co.,Ltd. |