CN112186249A - 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 power lithium battery is developed in the ternary and lithium iron system, 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 mainly comprising 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; the ternary material suffers from high cobalt price and high overall price (the high nickel material can reduce the BOM cost, but the process cost is increased). 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 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 (logistic 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 Li2Mn2O4The 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: firstly, the cost is sensitive; secondly, the energy density has certain requirements; and fields with low safety requirements, such as electric bicycles, low-speed vehicles and the like. 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 conventional non-aqueous electrolyte of the lithium ion battery 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 phosphoric acid imine lithium shown in the formula I is used as the additive of the electrolyte, so that a lithium battery applying 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,
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 was charged into a 1000mL three-necked flask, 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 was added under protection of an inert gas, the temperature was controlled to be-70 to 20 ℃ (for example, -65 ℃ (50 ℃ (30 ℃ (10 ℃ (0 ℃), 10 ℃ (15 ℃), etc.), 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 oxyfluoride was slowly fed, and the reaction was sufficiently carried out 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. And then adding 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 fluoro-malonic acid, reacting for 4 hours, filtering to remove solid impurities, and removing the solvent 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 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 bistetrafluorophosphorimide salt or a combination of at least two thereof.
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 also comprises other additives, wherein the other additives comprise ethylene 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, 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-hexanetrinitrile, toluene, 4-methyl ethylene sulfite, ethylene glycol, propylene, Any one or a combination of at least two of maleic anhydride, tris (trimethylsilyl) borate, tris (trimethylsilyl) phosphite, tris (trimethylsilyl) phosphate or 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% of the total mass of the lithium ion battery nonaqueous electrolyte solution.
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 LiNixCoyMnzL(1-x-y-z)O2、LiCoxL(1-x')O2、LiNixLyMn(2-x″-y')O4And Liz'MPO4At 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..
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
LiMn2O4The 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 100 wt%.
The solvent in the electrolyte was as follows Ethylene Carbonate (EC): diethyl carbonate (DEC): ethyl Methyl Carbonate (EMC) ratio 3: 2: 5(vol: vol: vol) ratio; additives 1 wt% Vinylene Carbonate (VC), 0.5 wt% 1, 3-Propane Sultone (PS); 12.5 wt% LiPF65 wt% of lithium difluorophosphoramidite fluoro malonate.
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 voltage2O4Artificial graphite), the 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:
the 200 th cycle capacity retention (%) was (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 voltage2O4Artificial 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 4.2V, 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 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 (%) -recovery capacity/initial capacity X100%
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 voltage2O4Artificial graphite), cutoff current 0.02C, and then constant current discharge to 3.0V with 1C at-20 ℃. 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 performance and the low temperature discharge performance of experimental examples 1 to 5 and comparative examples 1 to 4 were respectively measured at a low temperature discharge capacity retention ratio (%) (-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 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 (10)
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 electrolyte according to claim 1, wherein the lithium fluoromalonate difluoroimidyl phosphate is contained in an amount of 0.001 to 10%, preferably 0.01 to 5%, based on 100% by mass of the total electrolyte.
3. The lithium fluoromalonate difluoroimidyl phosphate-containing electrolyte according to claim 1 or 2, wherein the lithium salt is any one of or a combination of at least two of lithium hexafluorophosphate, lithium difluorosulfonimidyl phosphate, lithium bistrifluoromethylsulfonimidyl phosphate, 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;
preferably, the content of the lithium salt is 0.01% to 20% by total mass of the electrolyte solution as 100%.
4. The lithium fluoromalonate difluorophosphinimine phosphate electrolyte of any one of claims 1-3, wherein the solvent is an aprotic organic solvent;
preferably, the aprotic organic solvent is selected from any one or a combination of at least two 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;
preferably, the aprotic organic solvent is contained in an amount of 55 to 99.979% based on 100% by mass of the total electrolyte.
5. The lithium fluoromalonate difluorophosphinimine phosphate-containing electrolyte according to any one of claims 1 to 4, wherein the lithium ion battery nonaqueous electrolyte further comprises other additives, including ethylene carbonate, vinylene carbonate, fluoroethylene carbonate, vinyl sulfate, succinonitrile, adiponitrile, succinic anhydride, 1-propylphosphoric anhydride, N' -dicyclohexylcarbodiimide, triallyl phosphate, biphenyl, cyclohexylbenzene, fluorobenzene, triphenyl phosphite, toluene, 1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, methylene methanedisulfonate, 1, 3-propanesultone, 1, 4-butanesultone, 1, 3-propanesultone, 1-propanesultone, and 1-propanesultone, Any one or a combination of at least two of ethylene glycol dipropionitrile, 1,3, 6-hexanetricarbonitrile, toluene, 4-methyl ethylene sulfite, maleic anhydride, tris (trimethylsilyl) borate, tris (trimethylsilyl) phosphite, tris (trimethylsilyl) phosphate, or propylene sultone;
preferably, the content of the other additives is 0.01-15% of the total mass of the non-aqueous electrolyte of the lithium ion battery as 100%.
6. 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 malonato difluorophosphinimine phosphate-containing electrolyte solution according to any one of claims 1 to 5.
7. The lithium ion battery of claim 6, 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.
8. The lithium ion battery of claim 6 or 7, wherein the active material of the positive electrode is LiNixCoyMnzL(1-x-y-z)O2、LiCoxL(1-x')O2、LiNixLyMn(2-x”-y')O4And Liz'MPO4At 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..
9. The lithium ion battery of any of claims 6-8, wherein the active material of the negative electrode comprises elemental lithium metal, alloyed lithium, or a carbon material.
10. The lithium ion battery of any of claims 6-9, wherein the alloyed lithium comprises an alloy of any one or at least two of aluminum, zinc, silicon, tin, gallium, or antimony with lithium;
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.
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