CN112186249B - Electrolyte containing fluoro-malonic acid difluoro-lithium phosphate and lithium ion battery containing electrolyte - Google Patents
Electrolyte containing fluoro-malonic acid difluoro-lithium phosphate and lithium ion battery containing electrolyte Download PDFInfo
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Abstract
The invention provides an electrolyte containing fluoro-malonic acid difluoro-imine lithium and a lithium ion battery containing the electrolyte. The lithium battery using the electrolyte has lower impedance, higher conductivity, good thermal stability and chemical stability, and can solve the problem that the safety and high and low temperature of the non-aqueous electrolyte of the conventional lithium battery cannot be considered at the same time.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to an electrolyte containing fluoro malonic acid difluoro lithium phosphate and a lithium ion battery containing the electrolyte.
Background
While the mainstream battlefield of the ternary and lithium iron system is developed for the power lithium battery, the lithium manganate battery starts to erode in the market as a lithium battery system which has less market attention, and the lithium manganate battery initiates impact on the new energy passenger car market which mainly comprises lithium iron by relying on the improvement of cost advantage and performance. The application system of lithium manganate still uses plug-in hybrid as the main application field, and what is not neglected is that pure electric passenger car models mainly using lithium manganate possess 36 families, and the proportion in the vehicle models matched with lithium manganate reaches 17%. The lithium manganate is applied to the most new energy of the north gasoline in the pure electric passenger car models, and is applied to mansion Jinlong vehicles and south vehicles, and in addition, zhongtong, yutong, yangziang, ankai, shenlong, asian and the like are applied to the pure electric passenger car models. The lithium manganate has the following characteristics:
1. the lithium manganate has no noble metal and relatively low price; ternary materials suffer from high cobalt prices and high overall prices (high nickel materials can reduce BOM costs, but process costs increase). 2. The voltage platform of the lithium manganate battery is high and is about 3.75-3.8V, and the voltage platform of the ternary lithium manganate battery is low and is 3.6-3.7V. 3. The lithium manganate has a spinel structure, so that the safety is relatively good; the ternary material has a layered structure, is easy to mix and discharge lithium and nickel, and has poor safety (the higher the nickel content is, the worse the nickel content is). 4. In the most key gram volume, the lithium manganate is lower, and the ternary material is higher. 5. Lithium manganate batteries have particularly poor high-temperature properties, and therefore, lithium manganate doped ternary is used in industrial applications. Typically, such as LMO: NCM =7:3 (low cost, electric bicycle), LMO: NCM =5:5 or 3:7 (logistics car). Although the voltage platform of a pure lithium manganate system, such as a high-voltage lithium manganate material, is improved, the high-temperature performance is particularly poor, and the capacity attenuation is serious above 55 ℃. Easily generate Li 2 Mn 2 O 4 The spinel structure causes the voltage platform to be reduced, the stability is poor, the capacity is irreversibly attenuated, and the like. 6. After the lithium iron phosphate material is added, the overall cost is as follows: lithium manganate is less than lithium iron phosphate and less than lithium manganate. 7. The service life is general.
In conclusion, the characteristics of lithium manganate are relatively applicable to: (1) the cost is sensitive; (2) the energy density has certain requirements; (3) the safety requirement is not high, such as electric bicycle, low-speed car etc.. Therefore, in order to make lithium manganate occupy a place in the power market, the problem of poor high-temperature performance is solved first.
Accordingly, it is desirable in the art to develop an electrolyte and a lithium ion battery that can have better high temperature performance.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide an electrolyte containing fluoro malonic acid difluoro lithium phosphate and a lithium ion battery containing the electrolyte, wherein the electrolyte has better safety and better high and low temperature performance, and can solve the problem that the safety and high and low temperature of the existing lithium ion battery non-aqueous electrolyte cannot be compatible.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides an electrolyte containing lithium fluoro-malonate difluorophosphate imine, the electrolyte comprising a lithium salt, a solvent and an additive, the additive comprising lithium fluoro-malonate difluorophosphate imine represented by the following formula i:
in the invention, the fluorinated malonic acid difluoro phosphoimine lithium shown in the formula I is used as an additive of the electrolyte, so that a lithium battery using the electrolyte has lower impedance, higher electrical conductivity, good thermal stability and chemical stability.
In the present invention, the lithium fluoro-malonate difluorophosphoramidite can be synthesized according to the following synthesis route:
the specific synthetic steps are as follows,
a1000 mL three-necked flask is 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, and 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 is added under protection of an inert gas, the temperature is controlled to-70 to 20 ℃ (for example, -65 ℃ (50 ℃ (30 ℃), -10 ℃ (0 ℃), 10 ℃, 15 ℃, etc.), and 150 to 280 parts by weight (for example, 160 parts by weight, 200 parts by weight, 220 parts by weight, 240 parts by weight, 260 parts by weight, 280 parts by weight, etc.) of phosphorus trifluoride is slowly introduced, and the mixture is stirred to be reacted sufficiently for 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, 20 ℃, 30 ℃, 40 ℃, 50 ℃ and 60 ℃) to remove the side product of trimethyl fluorosilane. Then 200 to 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 fluoro-malonic acid is added for reaction for 4 hours, solid impurities are removed by filtration, and the solvent is removed by rotary evaporation to obtain fluoro-malonic acid difluoro-imine lithium phosphate.
The inventor can reasonably speculate the action mechanism of the fluorine-containing malonic acid difluoro phosphoric acid imine lithium with the structural formula I in the lithium ion battery: 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 fluoromalonate difluorophosphate is contained 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 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, the other additives comprise any one 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, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, methylene methanedisulfonate, 1,3-propanesultone, 1,4-butanesultone, 1,3-propanesultone, ethylene glycol dipropionitrile, 1,3,6-hexanetricarbonitrile, toluene, 4-methylsulfurous acid ethylene sulfite, maleic anhydride, tris (trimethylsilyl) borate, tris (trimethylsilyl) phosphite, tris (trimethylsilyl) phosphate or a combination of at least two of propylene 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 including a positive electrode, a negative electrode, a separator provided between the positive electrode and the negative electrode, and an electrolyte solution, wherein the electrolyte solution is the above-described electrolyte solution containing lithium difluoropropanedioic acid and difluorophosphinimine.
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 1,0 and less than or equal to 1,0 and less than or equal to z is more than or equal to 1,0 and less than or equal to x + y + z is more than or equal to 1,0 and less than or equal to x '. Ltoreq. 1,0.3 and less than or equal to x'. Ltoreq. 0.6,0.01 and less than or equal to y '. Ltoreq. 0.2,0.5 and less than or equal to z'. Ltoreq.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 electrolyte uses fluorinated malonic acid-containing difluorophosphinimine lithium as an additive, and can solve the problem that the safety and high and low temperatures of the conventional lithium ion battery non-aqueous electrolyte cannot be compatible, the capacity retention rate of the lithium battery manufactured by applying the electrolyte is more than 97% after 200 times of circulation at 45 ℃, the discharge capacity retention rate is more than 90% at the low temperature of-20 ℃, the capacity retention rate is more than 95% after 7 days of high-temperature storage at 60 ℃, the capacity recovery rate is more than 92%, the thick expansion rate is less than 5.7%, and the lithium battery applying 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
LiMn 2 O 4 The artificial graphite battery comprises a positive electrode, a negative electrode, a PE diaphragm and the electrolyte containing the fluoro-malonic acid difluoro-imine lithium phosphate prepared according to the invention, wherein the total weight of the electrolyte is 100wt%.
The solvent in the electrolyte is as follows as 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); 12.5wt.% LiPF 6 5wt% of lithium fluoromalonate difluorophosphate.
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 electrolyte 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 embodied by testing the capacity retention rate of the battery at 45 ℃ and 1C for N times, and the specific method comprises the following steps:
the battery is placed in an environment of 45 ℃, and the formed battery is charged to 4.2V (LiMn) by using a 1C constant current and constant voltage 2 O 4 Artificial graphite), the cut-off current was 0.02C, and then the discharge was made to 3.0V with a constant current of 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 calculation formula of the capacity retention rate after 200 cycles at 45 ℃ is as follows:
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 swell after 7 days of storage at 60 ℃ of the battery:
charging the formed battery to 4.2V (LiMn) at normal temperature by using a 1C constant current and constant voltage 2 O 4 Artificial graphite), the cutoff current was 0.02C, then 1C constant current was discharged to 3.0V, the initial discharge capacity of the battery was measured, then 1C constant current constant voltage was charged to 4.2V, the cutoff current was 0.01C, the initial thickness of the battery was measured, then the thickness of the battery was measured after the battery was stored at 60 ℃ for 7 days, then 1C constant current was discharged to 3.0V, the retention capacity of the battery was measured, then 1C constant current constant voltage was charged to 3.0V, the cutoff battery was 0.02C, then 1C constant current was discharged to 3.0V, and 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 (%) = recovered capacity/initial capacity × 100%
Battery thickness swelling ratio (%) = (thickness after 7 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 component capacity grading is charged to 4.2V (LiMn) by using a 1C constant current and constant voltage 2 O 4 Artificial graphite), cutoff current 0.02C, then constant current discharge to 3.0V at-20 deg.C with 1C. 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 97% after being cycled for 200 times at 45 ℃, the discharge capacity retention rate of more than 90% at the low temperature of-20 ℃, and the capacity retention rate of more than 95% after being stored for 7 days at the high temperature of 60 ℃, the capacity recovery rate of more than 92% and the thickness expansion rate of less than 5.7%.
The applicant states that the electrolyte containing lithium difluorophosphoramidite fluoromalonate and the lithium ion battery containing the electrolyte of the invention are illustrated by the above examples, but the invention is not limited to the above examples, which means that the invention can be implemented only by the above examples. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (16)
1. The electrolyte containing the lithium fluoromalonate difluorophosphate imine is characterized by comprising a lithium salt, a solvent and an additive, wherein the additive comprises the lithium fluoromalonate difluorophosphate imine shown as the following formula I:
2. the lithium fluoromalonate difluoroimidyl phosphate-containing electrolyte solution according to claim 1, wherein the lithium fluoromalonate difluoroimidyl phosphate is contained in an amount of 0.001 to 10% based on 100% by mass of the total electrolyte solution.
3. The lithium fluoromalonate difluorophosphate imide lithium electrolyte as claimed in claim 2, wherein the lithium fluoromalonate difluorophosphate imide lithium content is 0.01 to 5% by mass based on 100% by mass of the total electrolyte.
4. The lithium fluoromalonate difluorophosphate imide-based electrolyte according to claim 1, wherein the lithium salt is any one of or a combination of at least two 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 bis-tetrafluorophosphoryl imide salt.
5. The lithium fluoromalonate difluorophosphinite electrolyte according to claim 1, wherein the lithium salt is present in an amount of 0.01 to 20% based on 100% by weight of the total electrolyte.
6. The lithium fluoromalonate difluorophosphinite electrolyte of claim 1, wherein the solvent is an aprotic organic solvent.
7. The lithium fluoromalonate difluorophosphinite electrolyte of claim 6, wherein the aprotic organic solvent is selected from the group consisting of methyl propionate, methyl acetate, propyl propionate, methyl butyrate, ethyl butyrate, propyl acetate, butyl butyrate, acetonitrile, methylpropyl carbonate, ethyl propionate, γ -butyrolactone, sulfolane, dimethyl sulfoxide, tetrahydrofuran, propylene carbonate, ethyl acetate, diethyl carbonate, ethyl methyl carbonate, dimethyl carbonate, and ethylene carbonate, or a combination of at least two thereof.
8. The lithium fluoromalonate difluorophosphinite electrolyte according to claim 6, wherein the aprotic organic solvent is present in an amount of 55 to 99.979% based on 100% by weight of the total electrolyte.
9. The lithium fluorosulfonate difluorophosphinic acid imide electrolyte of claim 1 further comprising other additives including any one 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, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, methylene methanedisulfonate, 1,3-propanesultone, 1,4-butanesultone, 1,3-propensultone, ethylene glycol bispropionitrile, 1,3,6-hexanetricarbonitrile, toluene, 4-methylvinyl ester, ethylene sulfite, maleic anhydride, tris (trimethylsilyl) borate, tris (trimethylsilyl) phosphite, tris (trimethylsilyl) phosphate, or propene sultone.
10. The lithium fluoromalonate difluorophosphinite-containing electrolyte according to claim 9, wherein the content of the other additives is 0.01 to 15% based on 100% by mass of the total electrolyte.
11. A lithium ion battery comprising a positive electrode, a negative electrode, a separator provided between the positive electrode and the negative electrode, and an electrolyte solution, wherein the electrolyte solution is the lithium fluoro malonate difluorophosphate imide 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; 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 1,0 and less than or equal to 1,0 and less than or equal to z is more than or equal to 1,0 and less than or equal to x + y + z is more than or equal to 1,0 and less than or equal to x '. Ltoreq. 1,0.3 and less than or equal to x'. Ltoreq. 0.6,0.01 and less than or equal to y '. Ltoreq. 0.2,0.5 and less than or equal to z'. Ltoreq.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 lithium ion battery of claim 14, wherein the alloyed lithium comprises an alloy of lithium with any one or at least two of aluminum, zinc, silicon, tin, gallium, or antimony.
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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| 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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