CN112186254B - Electrolyte containing difluoro oxalic acid phosphoimide lithium and lithium ion battery using electrolyte - Google Patents
Electrolyte containing difluoro oxalic acid phosphoimide lithium and lithium ion battery using electrolyte Download PDFInfo
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides an electrolyte containing lithium difluoro oxalate phosphorus imide and a lithium ion battery using the electrolyte. The lithium difluorooxalato phosphoimide is used as an additive in the electrolyte, so that the problem that the safety and high and low temperatures of the conventional non-aqueous electrolyte of the lithium ion battery cannot be compatible is solved, and the lithium ion battery using the electrolyte has lower impedance, higher electrical conductivity, good thermal stability and chemical stability.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to an electrolyte containing lithium difluoro-oxalato-phosphoryl-imine and a lithium ion battery using the electrolyte.
Background
The lithium iron phosphate material is widely applied to lithium ion battery powered automobiles, and the lithium iron phosphate battery has the advantages of large volume, heavy weight, high safety and stability, high temperature resistance and good cycle performance, but the large volume is not beneficial to the use of household vehicles, the low-temperature discharge performance is poor, and the problems of low capacity and the like easily occur in areas with high latitude. The ternary material lithium battery is a ternary polymer lithium battery, and refers to a lithium battery taking nickel cobalt lithium manganate or nickel cobalt lithium aluminate as a positive electrode material. The ternary lithium battery has the advantages of smaller volume, light weight, higher energy density, low temperature resistance and better cycle performance, but the safety performance of the ternary lithium battery is not stable enough, which is the respective advantages and disadvantages of the lithium iron phosphate battery and the ternary lithium battery. The comprehensive performance of the ternary battery is superior to that of a lithium iron phosphate battery in the aspects of comprehensive energy density, cycle life, low-temperature performance and the like, but the lithium iron phosphate still has a firm position in stability and cost. It is difficult to say that the lithium iron phosphate battery and the ternary lithium battery are better, because the performance difference is caused by different materials, and finally the ternary lithium battery is more suitable for the development of future electric vehicles. The ternary material is really widely applied in the future, and firstly the problem of safety performance of the ternary material is solved, and meanwhile, high and low temperature performance is considered.
CN109824726A discloses a preparation method of lithium difluorobis-oxalate phosphate, a non-aqueous electrolyte and a battery, wherein the lithium difluorobis-oxalate phosphate has the following structure:
the non-aqueous electrolyte has good conductivity and stable electrochemistry, and the battery containing the non-aqueous electrolyte has high discharge rate and small internal resistance. However, lithium difluorooxalate phosphate is easy to generate gas, the content of free acid and chloride ions cannot be easily controlled in the preparation process at the same time of high and low temperature performance, the preparation method of lithium difluorooxalate phosphoimide protected by the invention is simple, the content of free acid and chloride ions is easy to control, the battery containing the non-aqueous electrolyte can be compatible with high and low temperature performance, and gas cannot be generated in the battery formation process and the charging and discharging process.
Therefore, in the art, it is desired to develop an electrolyte solution capable of achieving both high and low temperature performance to solve the safety problem of the battery.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide an electrolyte containing lithium phosphorodiamidite difluorinate and a lithium ion battery using the electrolyte. The electrolyte can solve the problem that the safety and high and low temperature of the non-aqueous electrolyte of the conventional lithium ion battery cannot be considered at the same time.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides an electrolyte containing lithium difluorooxalato phosphoimines, which comprises a lithium salt, a solvent and an additive, wherein the additive comprises lithium difluorooxalato phosphoimines shown in the following formula I:
in the invention, the lithium battery applying the electrolyte has lower impedance, higher electrical conductivity, good thermal stability and chemical stability.
In the invention, the lithium phosphoryl imido difluorooxalate shown in the formula I can be synthesized according to the following route:
the specific synthesis steps are as follows:
a1000 mL three-necked flask was charged with 300 to 600 parts by weight (for example, 350 parts by weight, 380 parts by weight, 400 parts by weight, 450 parts by weight, 480 parts by weight, 500 parts by weight, 550 parts by weight, 600 parts by weight, etc.) of methylene chloride, purged with an inert gas, charged with 100 to 200 parts by weight (for example, 120 parts by weight, 150 parts by weight, 180 parts by weight, 200 parts by weight, etc.) of lithium hexamethyldisilazide, controlled at-70 to 20 ℃ (for example, -70 ℃ (50 ℃,0 ℃, 10 ℃, 15 ℃, 20 ℃, etc.), slowly charged with 150 to 280 parts by weight (for example, 160 parts by weight, 180 parts by weight, 200 parts by weight, 230 parts by weight, 250 parts by weight, 270 parts by weight, etc.) of phosphorus trifluoride, and stirred for a sufficient reaction time of 3 to 8 hours (for example, 3 hours, 5 hours, 7 hours, etc.). After the reaction is finished, the temperature is raised to 20-60 ℃ (for example, 22 ℃, 25 ℃, 30 ℃, 40 ℃, 50 ℃,60 ℃ and the like) to remove the side product of trimethyl fluorosilane. Then 200-300 parts by weight (such as 220 parts by weight, 240 parts by weight, 260 parts by weight, 280 parts by weight and the like) of trimethylsilyl fluoromalonic acid is added for reaction for 4 hours, solid impurities are removed by filtration, and the solvent is removed by rotary evaporation to obtain lithium difluorooxalatophosphoryl imine.
The inventor can reasonably speculate the action mechanism of the lithium difluoro-oxalato-phosphoryl-imine in the lithium ion battery, which is shown in the structural formula I: mainly, the carbon-oxygen bond of the ring structure in the structural formula I is broken under a certain condition, condensation reaction occurs, films are formed at the positive electrode and the negative electrode simultaneously, the phosphate group can improve the high-temperature performance of the lithium battery, the fluorine element is favorable for improving the flash point of the electrolyte, the safety performance of the battery under heating and overcharging is improved, the transmission performance of lithium ions can be improved, the viscosity is adjusted, and the low-temperature discharge of the lithium battery is facilitated. In addition, the imide structure can attract hydrogen ions in the electrolyte, remove water and inhibit acid, and can be used for complexing metal ions dissolved out from the anode material together with carbonyl, so that the decomposition of the electrolyte catalyzed by the metal ions is further inhibited, and the generation of gas is inhibited.
Preferably, the lithium difluorooxalato phosphoryl imide is present in an amount of 0.001 to 10%, for example 0.001%, 0.003%, 0.008%, 0.01%, 0.02%, 0.03%, 0.05%, 0.08%, 0.1%, 0.5%, 0.8%, 1%, 2%, 3%, 5%, 7%, 9% or 10%, preferably 0.01 to 5%, based on 100% by mass of the total electrolyte.
Preferably, the lithium salt is any one of lithium hexafluorophosphate, lithium difluorosulfonimide, lithium bistrifluoromethylsulfonimide, lithium difluorophosphate, lithium difluorobis (oxalato) phosphate, lithium difluorooxalato phosphate, lithium bis (oxalato) borate, lithium difluorooxalato phosphate, lithium tetrafluoroborate, lithium iodide, lithium tetrafluorooxalato phosphate or lithium bis (tetrafluorophosphoryl) imide salt or a combination of at least two of them.
Preferably, the lithium salt is contained in an amount of 0.01% to 20%, for example, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, or 15% based on 100% of the total mass of the electrolyte.
Preferably, the solvent is an aprotic organic solvent.
Preferably, the aprotic organic solvent is selected from any one of methyl propionate, methyl acetate, propyl propionate, methyl butyrate, ethyl butyrate, propyl acetate, butyl butyrate, acetonitrile, methyl propyl carbonate, ethyl propionate, γ -butyrolactone, sulfolane, dimethyl sulfoxide, tetrahydrofuran, propylene carbonate, ethyl acetate, diethyl carbonate, methyl ethyl carbonate, dimethyl carbonate, or ethylene carbonate, or a combination of at least two thereof.
Preferably, the aprotic organic solvent is contained in an amount of 55% to 99.979%, for example, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 99%, etc., based on 100% by mass of the total electrolyte.
Preferably, the lithium ion battery non-aqueous electrolyte further comprises other additives, wherein the other additives comprise ethylene carbonate, vinylene carbonate, fluoroethylene carbonate, vinyl sulfate, succinonitrile, adiponitrile, succinic anhydride, 1-propyl phosphoric anhydride, N' -dicyclohexylcarbodiimide, triallyl phosphate and tripropargyl phosphate, biphenyl, cyclohexylbenzene, fluorobenzene, triphenyl phosphite, toluene, 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether, methylene methanedisulfonate, 1, 3-propane sultone, 1, 4-butane sultone, 1, 3-propene sultone, ethylene glycol bispropionitrile, 1,3, 6-hexanetrinitrile, toluene, 4-methyl vinyl sulfite, ethylene sulfite, maleic anhydride, tris (trimethylsilyl) borate, tris (trimethylsilyl) phosphite, tris (trimethylsilyl) phosphate, or propene sultone.
Preferably, the content of the other additive is 0.01 to 15%, for example, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, or 15% based on 100% by mass of the total nonaqueous electrolyte solution of the lithium ion battery.
In another aspect, the present invention provides a lithium ion battery, which includes a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is the above electrolyte containing lithium difluorooxalato phosphoryl imine.
Preferably, the positive electrode and the negative electrode include an active material, a conductive agent, a current collector, and a binder for binding the active material with the conductive agent and the current collector.
Preferably, the active material of the positive electrode is LiNi x Co y Mn z L (1-x-y-z) O 2 、LiCo x L (1-x') O 2 、LiNi x L y Mn (2-x″-y') O 4 And Li z' MPO 4 At least one of; wherein L is at least one of Co, al, sr, mg, ti, ca, zr, zn, si and Fe; m is at least one of Fe, mn and Co; 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, x + y + z is more than or equal to 0 and less than or equal to 1, x ' is more than or equal to 0.3 and less than or equal to 0.6, y ' is more than or equal to 0.01 and less than or equal to 0.2, and z ' is more than or equal to 0.5 and less than or equal to 1.
Preferably, the active material of the negative electrode includes elemental lithium metal, alloyed lithium, or a carbon material.
Preferably, the alloyed lithium comprises an alloy of lithium with any one or at least two of aluminum, zinc, silicon, tin, gallium or antimony.
Preferably, the carbon material is any one of natural graphite, graphitized coke, graphitized MCMB, graphitized mesophase pitch carbon fiber or a combination of at least two of the same.
Compared with the prior art, the invention has the following beneficial effects:
the lithium battery manufactured by the electrolyte has a discharge capacity retention rate of more than 90 percent at a low temperature of-20 ℃, a capacity retention rate of more than 95 percent after being stored for 30 days at a high temperature of 60 ℃, a capacity recovery rate of more than 80 percent, a thickness expansion rate of less than 6.7 percent and a capacity retention rate of more than 95 percent after being cycled for 200 times at 45 ℃, and the lithium battery using the electrolyte has lower impedance, higher conductivity, good thermal stability and chemical stability.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
LiNi 0.8 Co 0.1 Mn 0.1 O 2 The artificial graphite battery comprises a positive electrode, a negative electrode, a diaphragm and phosphorus oxyfluoride-containing phosphorus oxyfluoride prepared according to the inventionThe electrolyte of lithium imide, and the total weight of the electrolyte containing lithium phosphoimide difluoro oxalate is 100wt%.
The solvent in the electrolyte is as follows Ethylene Carbonate (EC): diethyl carbonate (DEC): ethyl Methyl Carbonate (EMC) ratio 3:2:5 (vol: vol: vol) ratio; 1wt% of Vinylene Carbonate (VC), 0.5wt% of 1, 3-Propane Sultone (PS); adding 12.5wt% of LiPF 6 And 5wt% lithium phosphoamidite.
Examples 2 to 5 and comparative examples 1 to 5
Examples 2 to 5 and comparative examples 1 to 5 were the same as example 1 except that the lithium salt of the electrolytic solution and the additive were different. Specifically, the results are shown in Table 1.
TABLE 1
The experimental examples 1 to 5 and the comparative examples 1 to 5 were respectively tested for high-temperature cycle performance and high-temperature storage performance, and the test indexes and test methods were as follows:
(1) The high-temperature cycle performance is shown by testing the capacity retention rate of the battery at 45 ℃ for N times at 1C, and the specific method comprises the following steps:
the battery is placed in an environment of 45 ℃, and the formed battery is charged to 4.45V (LiNi) by using a 1C constant current and constant voltage 0.8 Co 0.1 Mn 0.1 O 2 Artificial graphite), the cutoff current was 0.02C, and then constant current discharge was performed to 3.0V with 1C. After such charge/discharge cycles, the capacity retention rate after 200 weeks' cycles was calculated to evaluate the high-temperature cycle performance thereof.
The capacity retention rate after 200 cycles at 45 ℃ is calculated according to the following formula:
capacity retention ratio (%) at 200 cycles = (200 th cycle discharge capacity/1 st cycle discharge capacity) × 100%
(2) High temperature storage performance-by testing the capacity retention, capacity recovery and thickness expansion of the battery after 30 days storage at 60 ℃:
charging the formed battery to 4.45V (LiNi) at normal temperature by using a 1C constant current and constant voltage 0.8 Co 0.1 Mn 0.1 O 2 Artificial graphite), the cutoff current was 0.02C, then 1C constant current discharge to 3.0V, the initial discharge capacity of the battery was measured, then 1C constant current constant voltage charge to 4.45V, the cutoff current was 0.01C, the initial thickness of the battery was measured, then the thickness of the battery was measured after storing the battery at 60 ℃ for 30 days, then 1C constant current discharge to 3.0V, the retention capacity of the battery was measured, then 1C constant current constant voltage charge to 3.0V, the cutoff battery was 0.02C, then 1C constant current discharge to 3.0V, the recovery capacity was measured.
The calculation formulas of the capacity retention rate, the capacity recovery rate and the thickness expansion are as follows:
battery capacity retention (%) = retention capacity/initial capacity × 100%
Battery capacity recovery rate (%) = recovered capacity/initial capacity × 100%
Battery thickness swelling ratio (%) = (thickness after 30 days-initial thickness)/initial thickness × 100%
(3) The low-temperature discharge performance is shown by testing the discharge capacity retention rate of the battery at the temperature of-20 ℃ and 1C, and the specific method comprises the following steps:
the battery is placed in an environment of 25 ℃, and the battery after the component capacity division is charged to 4.45V (LiNi) by using a 1C constant current and a constant voltage 0.8 Co 0.1 Mn 0.1 O 2 Artificial graphite), the cut-off current was 0.02C, and then discharge was performed at-20℃ with a constant current of 1C to 3.0V. The calculation formula of the discharge capacity retention rate at-20 ℃ is as follows:
the test results of the high temperature cycle performance, the high temperature storage and the low temperature discharge performance of experimental examples 1 to 5 and comparative examples 1 to 4 were respectively measured by using the low temperature discharge capacity retention (%) = (-20 ℃ discharge capacity/1 st normal temperature discharge capacity) × 100%, and are shown in table 2.
TABLE 2
Through testing the high-temperature cycle, high-temperature storage and low-temperature discharge performance of the lithium battery prepared in the embodiment, the lithium battery prepared by applying the electrolyte disclosed by the invention is found to have the capacity retention rate of more than 90% at the low temperature of-20 ℃ and the capacity recovery rate of more than 80% at the high temperature of 60 ℃ for 30 days, the capacity retention rate of more than 95%, the thickness expansion rate of less than 6.7% and the capacity retention rate of more than 95% at the 45 ℃ cycle for 200 times.
The applicant states that the present invention is illustrated by the above examples of the lithium phosphorus oxydifluoride imide phosphate-containing electrolyte and the lithium ion battery using the same, but the present invention is not limited to the above examples, i.e., the present invention is not limited to the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (16)
1. An electrolyte containing lithium phosphoamidite, which is characterized by comprising a lithium salt, a solvent and an additive, wherein the additive comprises lithium phosphoamidite shown as the following formula I:
2. the lithium difluorooxalato phosphorylimine lithium-containing electrolyte solution according to claim 1, wherein the lithium difluorooxalato phosphorylimine lithium content is 0.001 to 10% by mass of the total mass of the electrolyte solution being 100%.
3. The lithium difluorooxalato phosphorylimine lithium-containing electrolyte solution according to claim 2, wherein the lithium difluorooxalato phosphorylimine lithium content is 0.01 to 5% based on 100% of the total mass of the electrolyte solution.
4. The lithium difluorooxalato phosphorylimide salt-containing electrolyte solution of claim 1, wherein the lithium salt is any one of lithium hexafluorophosphate, lithium difluorosulfonylimide, lithium bistrifluoromethylsulfonylimide, lithium difluorophosphate, lithium difluorobisoxalato phosphate, lithium difluorooxalato phosphate, lithium bisoxalato borate, lithium difluorooxalato phosphate, lithium tetrafluoroborate, lithium iodide, lithium tetrafluorooxalato phosphate, or a combination of at least two of them.
5. The lithium difluorooxalato phosphoryl imine lithium-containing electrolyte solution according to claim 1, wherein the content of the lithium salt is 0.01% to 20% based on 100% of the total mass of the electrolyte solution.
6. The lithium phosphoryl imine difluoride oxalate-containing electrolyte according to claim 1, characterized in that the solvent is an aprotic organic solvent.
7. The lithium phosphorodiamidite-containing electrolyte according to claim 6, wherein the aprotic organic solvent is selected from any one of methyl propionate, methyl acetate, propyl propionate, methyl butyrate, ethyl butyrate, propyl acetate, butyl butyrate, acetonitrile, methyl propyl carbonate, ethyl propionate, γ -butyrolactone, sulfolane, dimethyl sulfoxide, tetrahydrofuran, propylene carbonate, ethyl acetate, diethyl carbonate, ethyl methyl carbonate, dimethyl carbonate, or ethylene carbonate, or a combination of at least two thereof.
8. The lithium phosphorodiamidite difluoride oxalate according to claim 6, wherein the aprotic organic solvent is present in an amount of 55 to 99.979% based on 100% of the total mass of the electrolyte.
9. The lithium difluorophthalimide phosphate-containing electrolyte of claim 1, wherein the electrolyte further comprises other additives, the other additives comprising any one of or a combination of at least two of ethylene carbonate, vinylene carbonate, fluoroethylene carbonate, vinyl sulfate, succinonitrile, adiponitrile, succinic anhydride, 1-propylphosphoric anhydride, N' -dicyclohexylcarbodiimide, triallyl phosphate, tripropargyl phosphate, biphenyl, cyclohexylbenzene, fluorobenzene, triphenyl phosphite, toluene, 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether, methylene methanedisulfonate, 1, 3-propanesultone, 1, 4-butanesultone, 1, 3-propanesultone, ethylene glycol dipropionitrile, 1,3, 6-hexanetricarbonitrile, toluene, 4-methylethenesulfite, ethylene sulfite, maleic anhydride, tris (trimethylsilyl) borate, tris (trimethylsilyl) phosphite, tris (trimethylsilyl) phosphate, or propene sultone.
10. The lithium difluorooxalato phosphoryl imine lithium-containing electrolyte solution according to claim 9, characterized in that the content of the other additives is 0.01 to 15% based on 100% of the total mass of the electrolyte solution.
11. A lithium ion battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte solution, wherein the electrolyte solution is the lithium difluorooxalato phosphoryl imine-containing electrolyte solution according to any one of claims 1 to 10.
12. The lithium ion battery of claim 11, wherein the positive and negative electrodes comprise an active material, a conductive agent, a current collector, and a binder that binds the active material to the conductive agent and the current collector.
13. The lithium ion battery of claim 11, wherein the active material of the positive electrode is LiNi x Co y Mn z L (1-x-y-z) O 2 、LiCo x L (1-x') O 2 、LiNi x L y Mn (2-x”-y') O 4 And Li z' MPO 4 At least one of (a); wherein L is at least one of Co, al, sr, mg, ti, ca, zr, zn, si and Fe; m is at least one of Fe, mn and Co; 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, x + y + z is more than or equal to 0 and less than or equal to 1, x ' is more than or equal to 0.3 and less than or equal to 0.6, y ' is more than or equal to 0.01 and less than or equal to 0.2, and z ' is more than or equal to 0.5 and less than or equal to 1.
14. The lithium ion battery of claim 11, wherein the active material of the negative electrode comprises elemental lithium metal, alloyed lithium, or a carbon material.
15. The li-ion battery of claim 14, wherein the alloyed lithium comprises an alloy of any one or at least two of aluminum, zinc, silicon, tin, gallium, or antimony with lithium.
16. The lithium ion battery of claim 14, wherein the carbon material is any one of natural graphite, graphitized coke, graphitized MCMB, graphitized mesophase pitch carbon fiber, or a combination of at least two thereof.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016002481A1 (en) * | 2014-07-01 | 2016-01-07 | セントラル硝子株式会社 | Electrolyte solution for nonaqueous electrolyte batteries, and nonaqueous electrolyte battery using same |
| WO2019146705A1 (en) * | 2018-01-24 | 2019-08-01 | セントラル硝子株式会社 | Electrolyte for non-aqueous electrolyte battery, and non-aqueous electrolyte battery using said electrolyte |
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Patent Citations (2)
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| WO2016002481A1 (en) * | 2014-07-01 | 2016-01-07 | セントラル硝子株式会社 | Electrolyte solution for nonaqueous electrolyte batteries, and nonaqueous electrolyte battery using same |
| WO2019146705A1 (en) * | 2018-01-24 | 2019-08-01 | セントラル硝子株式会社 | Electrolyte for non-aqueous electrolyte battery, and non-aqueous electrolyte battery using said electrolyte |
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| CN112186254A (en) | 2021-01-05 |
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