CN111755747B - Non-aqueous electrolyte, battery containing non-aqueous electrolyte and vehicle containing battery - Google Patents
Non-aqueous electrolyte, battery containing non-aqueous electrolyte and vehicle containing battery Download PDFInfo
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- CN111755747B CN111755747B CN201910246456.9A CN201910246456A CN111755747B CN 111755747 B CN111755747 B CN 111755747B CN 201910246456 A CN201910246456 A CN 201910246456A CN 111755747 B CN111755747 B CN 111755747B
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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
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- 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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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Abstract
The invention discloses a non-aqueous electrolyte, a battery containing the non-aqueous electrolyte and a vehicle containing the battery. When the electrolyte is applied to a battery, the additive can form a film on the surfaces of a positive electrode and a negative electrode at the same time, and the battery still shows good cycle performance at a high voltage of 4.95V, so that the electrolyte shows better high-temperature stability and high-pressure stability than the electrolyte added with the film-forming additive in the prior art.
Description
Technical Field
The present invention relates to the field of nonaqueous electrolytic solutions, and particularly to a nonaqueous electrolytic solution, a battery containing the same, and a vehicle containing the battery.
Background
Since the 90 s of the 20 th century, lithium ion secondary batteries have reached a rapid development from birth. Generally, a lithium ion battery with a non-aqueous solute includes a lithium negative electrode, a lithium salt dissolved in an organic solvent, and an electrochemically active positive electrode material. During charging, lithium ions migrate from the positive electrode through the electrolyte to the negative electrode, while during discharging they flow in the opposite direction. In recent years, secondary lithium ion batteries with high energy density have been the subject of attention, and therefore, new active materials that can be used as secondary lithium batteries have been also noticed. Under the continuous reform and update of power batteries, more and more battery materials with higher energy density and higher application voltage are paid more and more attention, the electrolyte matched with a high-energy-density electrode material also becomes important, and the problem of the operation of the battery under high voltage is that the electrolyte can have parasitic reaction (generally oxidation decomposition reaction) with an anode interface, so that the service life of the battery is reduced. The key point of continuous research at present is to promote the oxidative decomposition potential of the electrolyte and to form a film on the surface of the anode to hinder the decomposition of the electrolyte under the influence of an anode interface, wherein the oxidative decomposition potential of the electrolyte is mainly promoted by seeking a novel solvent or an additive, so that the oxidative stability of the whole electrolyte system is reduced or reduced, the overall stability of the electrolyte is further promoted, the reduction of the oxidative reaction reduces the decomposition of the electrolyte, the sufficiency of the electrolyte in the circulating process is ensured, and the service life of the battery is prolonged; the latter is mostly electrolyte of additive type, choose one or several sacrificial additives, can take place oxidative decomposition reaction and form a membranous layer that can hinder electrolyte and anodal side reaction in advance before the electrolyte takes place to decompose, hinder the further decomposition of electrolyte, in order to promote the life-span of the battery.
The research of novel high voltage electrolyte is numerous, use the current system of novel solvent replacement more, have certain problem, if the conductivity is low, or have shortcomings such as viscosity big, and it is also a good compromise to use the additive to improve, present most additive all uses the oxidative decomposition electric potential that improves whole electrolyte system as the starting point, therefore can have in the electrolyte a small amount of solvent still can oxidative decomposition's possibility under the high potential to cause the electrolyte finally still to be consumed totally, cause the battery cycle in-process to take place the capacity and jump water. The positive electrode film forming additive also has the defects that the film layer is damaged due to the corrosion of the electrolyte when contacting with the electrolyte.
Disclosure of Invention
In order to solve the above problems, the present application provides a nonaqueous electrolytic solution including a lithium salt, a first organic solvent, and a first additive, the first additive having the following structural formula:
wherein, R1, R2, R3 and R4 are respectively and independently selected from one of hydrogen atom, alkyl, halogenated alkyl, alkoxy and halogen atom; r5 is selected from one of alkyl, haloalkoxy, phenyl and halophenyl; wherein the halogen is F, Cl, Br and I; n is 0 to 5 and is an integer.
Optionally, R1, R2, R3 and R4 are independently selected from alkyl with 1-5 carbon atoms, halogenated alkyl with 1-5 carbon atoms and alkoxy with 1-5 carbon atoms; r5 is one selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, a haloalkoxy group having 1 to 5 carbon atoms, a phenyl group and a halophenyl group.
Optionally, the first additive is one or more of 4- (3, 5-dimethylpyridin-4-yl) phenyl trifluoroacetate, 4- (3, 5-dimethylpyridin-4-yl) phenyl trifluoropropionate, 4- (3, 5-dimethylpyridin-4-yl) phenyl trimethyi-noate, 4- (3, 5-dimethylpyridin-4-yl) benzyl trifluoroacetate, and 4- (3, 5-dimethylpyridin-4-yl) benzyl trifluoropropionate.
Optionally, the content of the additive is 0.1-10% based on the total mass of the nonaqueous electrolyte.
Optionally, the nonaqueous electrolyte further contains a second additive, and the second additive includes one or more of 1, 3-propane sultone, 1, 4-butane sultone, propenyl-1, 3-sultone, ethylene sulfate, propylene sulfate, butylene sulfite, vinylene carbonate, fluoroethylene carbonate, lithium bis (fluorosulfonyl) imide in bis (oxalato) borate.
Optionally, the content of the second additive is 0.05% to 20% based on the total mass of the nonaqueous electrolyte.
Optionally, the first organic solvent is one or more selected from dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, dipropyl carbonate, ethylene carbonate, propylene carbonate, vinylene carbonate, gamma-butyrolactone, sultone, ethylene sulfite, propylene sulfite, methyl sulfide, diethyl sulfite, methyl formate, methyl acrylate, methyl butyrate and ethyl acetate.
Optionally, the lithium salt is selected from one or more of LiBOB, LiPF6, LiBF4, LiSbF6, LiClO4, LiCF3SO3, Li (CF3SO2)2N, LiC4F9SO3, LiAlO4, LiAsF6, LiAlCl4, LiCl, LiI and low fatty acid lithium carbonate, and the concentration of the lithium salt is 0.3 to 3 mol/L.
A second object of the present invention is to provide a battery including a battery case, and a cell and a nonaqueous electrolytic solution sealed in the battery case, the cell including a positive electrode, a negative electrode, and a separator, wherein the nonaqueous electrolytic solution is the above-mentioned nonaqueous electrolytic solution.
A third object of the invention is to provide a vehicle that contains the above battery.
Compared with the prior art, the invention has the beneficial effects that: the first additive is added into the non-aqueous electrolyte, the non-aqueous electrolyte is applied to a battery, the battery has good cycle performance under the high voltage of 4.95V, films can be formed on the surfaces of a positive electrode and a negative electrode at the same time, the structure of the first additive can prevent the electrolyte and other harmful substances from contacting with the films, the degradation of the electrolyte can be effectively reduced, the positive electrode and the negative electrode are protected from being influenced, the content of the electrolyte and the stability of an electrode material are ensured, and the service life of the battery is prolonged.
Detailed Description
The application provides a nonaqueous electrolyte, which contains a lithium salt, a first organic solvent and a first additive, wherein the first additive has the following structural formula:
wherein, R1, R2, R3 and R4 are respectively and independently selected from one of hydrogen atom, alkyl, halogenated alkyl, alkoxy and halogen atom; r5 is selected from one of alkyl, haloalkoxy, phenyl and halophenyl; wherein the halogen is F, Cl, Br and I; n is 0 to 5 and is an integer.
The molecular structure of the first additive used in the invention contains two functional groups of pyridine and ester group, and the two functional groups are distributed at two ends of the structure. Such additives are capable of undergoing redox on the electrode in preference to the solvent. When the ester group at one end is reduced to form a film on the negative electrode, the unreacted pyridine part at the other end can effectively prevent electrolyte solvent molecules from approaching the negative electrode, and can complex transition metal ions and acidic substances to prevent the transition metal ions and the acidic substances from depositing and damaging active materials on the negative electrode. When pyridine at one end is oxidized on the anode to form a film, unreacted ester group at the other end can also effectively prevent electrolyte solvent molecules from approaching the anode and consuming hydrofluoric acid (HF) generated in a system, so that the contact of the electrolyte and the anode and cathode film layers is blocked, the anode and cathode film layers are protected, the decomposition of the electrolyte is inhibited, and the cycle life of the battery is effectively prolonged.
According to the nonaqueous electrolytic solution provided by the present application, in the structural formula of the first additive, R1, R2, R3 and R4 may be the same or different, and the present application is not particularly limited.
When R1, R2, R3 and R4 are each independently selected from alkyl groups, they may be chain haloalkyl groups or cyclic alkyl groups, and the chain alkyl groups may be branched or straight-chain; preferably, an alkyl group having 1 to 5 carbon atoms is selected, and as examples of the alkyl group, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an n-pentyl group, an isopentyl group, and the like can be cited.
When R1, R2, R3 and R4 are each independently selected from haloalkyl groups, they may be a chain haloalkyl group or a cyclic haloalkyl group, and the chain haloalkyl group may be branched or straight; preferably, a halogenated alkyl group with the carbon number of 1-5 is selected, and further preferably, the halogenated alkyl group is a halogenated methyl group or a halogenated ethyl group, and after a plurality of experiments, the inventor of the application finds that the carbon chain length is related to the solubility, the longer the carbon chain is, the higher the non-polarity degree of the additive is, while the electrolyte is highly polar, and according to the principle of similar compatibility, the carbon chain length of the additive is too long, and the solubility of the additive is deteriorated; when the alkyl group is substituted with a halogen atom, all or part of the hydrogen atoms may be substituted.
As examples of the haloalkyl group, there may be mentioned trifluoromethyl, 2-fluoroethyl, 3-fluoro-n-propyl, 2-fluoroisopropyl, 4-fluoro-n-butyl, 3-fluoro-sec-butyl, 5-fluoro-n-pentyl, 4-fluoro-isopentyl and the like, and in the above specific examples, F may be substituted with Cl or Br or I.
When R1, R2, R3, and R4 are each independently selected from alkoxy groups, they may be chain alkoxy groups or cyclic alkoxy groups, and the chain alkoxy groups may be branched or straight; preferably, an alkoxy group having 1 to 5 carbon atoms is selected, and as examples of the alkoxy group, specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, n-pentoxy group, isopentoxy group, etc. can be mentioned, and it has been found through many experiments that the film forming property of the first additive is more preferable when the alkoxy group is more preferably one of methoxy group, ethoxy group and propoxy group.
When R5 is selected from alkyl, reference is made to the above description and no further description is given here.
When R5 is selected from haloalkoxy, it may be a chain haloalkoxy group, or a cyclic haloalkoxy group, and the chain haloalkoxy group may be branched or linear; preferably, the halogenated alkoxy group with the carbon number of 1-5 is selected, and further preferably, the halogenated alkoxy group is halogenated methoxy or halogenated ethoxy, and after a plurality of experiments, the inventor of the application finds that the carbon chain length is related to the solubility, the longer the carbon chain is, the higher the non-polarity degree of the additive is, while the electrolyte is highly polar, and according to the principle of similar compatibility, the carbon chain length of the additive is too long, and the solubility of the additive is deteriorated; when the halogen atom is substituted for the alkoxy group, all or part of the hydrogen atoms may be substituted.
As examples of the haloalkoxy group, there may be specifically mentioned trifluoromethoxy, 2-fluoroethoxy, 3-fluoro-n-propoxy, 2-fluoro-isopropoxy, 4-fluoro-n-butoxy, 3-fluoro-sec-butoxy, 5-fluoro-n-pentyloxy, 4-fluoro-isopentyloxy and the like, and in the above specific examples, F may be substituted by Cl or Br or I.
When R5 is selected from the group consisting of halophenyl, it may be ortho-substituted, meta-substituted or para-substituted, and the present application is not particularly limited.
Specifically, the first additive is one or more of 4- (3, 5-dimethylpyridin-4-yl) phenyl trifluoroacetate, - (3, 5-dimethylpyridin-4-yl) phenyl trifluoropropionate, 4- (3, 5-dimethylpyridin-4-yl) phenyl trimethyi-noate, 4- (3, 5-dimethylpyridin-4-yl) benzyl trifluoroacetate, and 4- (3, 5-dimethylpyridin-4-yl) benzyl trifluoropropionate.
According to the nonaqueous electrolytic solution of the present invention, one kind of the first additive may be added alone, or a plurality of kinds of the first additives may be added simultaneously. The content of the first additive is 0.1-10% based on the total mass of the non-aqueous electrolyte, and the first additive with the content is added into the electrolyte, so that a good film forming effect can be achieved, and the performance of the battery cannot be greatly influenced.
According to the nonaqueous electrolytic solution of the present invention, preferably, the nonaqueous electrolytic solution further contains a second additive, and the second additive includes at least one of 1,3 propane sultone, 1,4 butane sultone, propenyl-1, 3-sultone, vinyl sulfate, propylene sulfate, butylene sulfite, vinylene carbonate, fluoroethylene carbonate, lithium bis (fluorosulfonyl) imide. The additive and the film forming additive are jointly applied to the electrolyte, so that the stability of the battery is better.
The content of the second additive can be 0.05-20 wt% relative to 100 wt% of the nonaqueous solvent, the second additive can promote the first additive to form a stable SEI film on the surface of the negative electrode, and can protect the negative electrode, so that the cycle performance of the battery is further improved, but the second additive is excessively added to cause excessive consumption of active lithium.
According to the provided nonaqueous electrolytic solution of the present invention, the first organic solvent may use a nonaqueous solvent conventionally used by those skilled in the art, and may include, for example, one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, dipropyl carbonate, ethylene carbonate, propylene carbonate, vinylene carbonate, γ -butyrolactone, sultone, ethylene sulfite, propylene sulfite, methyl sulfide, diethyl sulfite, methyl formate, methyl acrylate, methyl butyrate, and ethyl acetate.
The nonaqueous electrolytic solution according to the present invention, wherein the selection of the lithium salt is not particularly required, may be a lithium salt conventionally used in a nonaqueous electrolytic solution, and may include, for example, one or more of LiBOB, LiPF6, LiBF4, LiSbF6, LiClO4, LiCF3SO3, Li (CF3SO2)2N, LiC4F9SO3, LiAlO4, LiAsF6, LiAlCl4, LiCl, LiI, and low-fatty-acid lithium carbonate. The concentration of the lithium salt is known to those skilled in the art and is generally 0.3 to 3mol/L, preferably 0.8 to 1.2 mol/L.
The first additive described herein can be prepared by the following steps.
Uniformly mixing halogenated pyridine, ester group substituted phenylboronic acid, an alkaline solution and a catalyst in a second solvent, heating and refluxing under the protection of inert gas, reacting for 12-24 h, cooling, extracting, drying and purifying to obtain the first additive.
The halogenated pyridine is one of bromopyridine, fluoropyridine, iodopyridine and chloropyridine, bromopyridine is preferred, the reaction activity is high, and the raw materials are easy to obtain.
The alkaline solution is one or more of sodium carbonate, sodium bicarbonate and cesium carbonate, and the purpose of the alkaline solution is to neutralize acidic byproducts in reaction products in time so as to promote the whole reaction system to proceed.
The catalyst is one or more of tetrakis (triphenylphosphine) palladium and palladium acetate.
The second solvent is one or more of toluene and tetrahydrofuran.
The inert gas is one or more of argon and nitrogen.
The preparation method of the non-aqueous electrolyte provided by the invention is a method conventionally used by those skilled in the art, namely, the components (including the lithium salt, the non-aqueous solvent, the first additive and/or the second additive) are uniformly mixed, and the mixing mode and the mixing sequence are not particularly limited in the invention. For example, the first organic solvent may be mixed uniformly, then the lithium salt may be added and mixed uniformly, and then the first additive may be added and mixed uniformly, or the second additive may be added together with the first additive.
The invention also provides a power battery which comprises a battery shell, and a battery core and a non-aqueous electrolyte which are sealed in the battery shell.
The nonaqueous electrolyte solution is the nonaqueous electrolyte solution, and the battery cell comprises a positive electrode, a negative electrode and a diaphragm. Since the present invention relates to only the improvement of the nonaqueous electrolyte of the battery in the prior art, other compositions and structures of the battery are not particularly limited, and are well known to those skilled in the art, and will not be described herein again.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
(1) Preparation of the first additive
Dissolving 3, 5-dimethyl-4-bromopyridine, 4- (trifluoroacetate) phenylboronic acid and tetrakis (triphenylphosphine) palladium in toluene, uniformly mixing, then adding a sodium carbonate aqueous solution (2.0mol/L), and refluxing for 24 hours under the protection of argon (inert gas), wherein the reaction temperature is 120 ℃. After the reaction is finished, cooling the mixture solution to room temperature, extracting with ethyl acetate, drying an organic phase with anhydrous magnesium sulfate, spin-drying a solvent to obtain a crude product, and separating by column chromatography to obtain a pure product of 4- (3, 5-dimethylpyridine-4-yl) phenyl trifluoroacetate, wherein the structural formula of the pure product is as follows:
(2) preparation of nonaqueous electrolyte:
the nonaqueous electrolyte solution for the lithium ion battery of this example was obtained by uniformly mixing Ethylene Carbonate (EC) and diethyl carbonate (DEC) in a mass ratio of 1:1 in an argon glove box to obtain a nonaqueous solvent, dissolving 12% by weight of lithium hexafluorophosphate (LiPF6) in 100% by weight of the nonaqueous solvent, and adding 0.1% by weight of 4- (3, 5-dimethylpyridin-4-yl) phenyltrifluoroacetate thereto, and was designated as C1.
(3) Preparing a lithium ion battery:
mixing a positive electrode active substance (LiNi0.5Mn1.5O4), acetylene black and polyvinylidene fluoride according to a mixture ratio of 90: 5: 5, uniformly mixing, and pressing on an aluminum foil to obtain a positive plate; taking a metal lithium sheet as a negative plate; the button cell S1 is prepared by taking a PE/PP composite diaphragm as an ion exchange membrane, adopting the non-aqueous electrolyte C1 of the embodiment and adopting a conventional method in the field.
Example 2
Preparation of the first additive:
dissolving 3, 5-dimethyl-4-bromopyridine, 4- (trifluoropropionate) phenylboronic acid and tetrakis (triphenylphosphine) palladium in toluene, uniformly mixing, then adding a sodium carbonate aqueous solution (2.0mol/L), and refluxing for 24 hours under the protection of argon (inert gas), wherein the reaction temperature is 120 ℃. After the reaction is finished, cooling the mixture solution to room temperature, extracting with ethyl acetate, drying an organic phase with anhydrous magnesium sulfate, spin-drying a solvent to obtain a crude product, and separating by column chromatography to obtain a pure product of 4- (3, 5-dimethylpyridine-4-yl) phenyl trifluoropropionate, wherein the structural formula of the pure product is as follows:
nonaqueous electrolyte and button cells were prepared by the same procedure as in example 1, except that: in the step (2), 0.1% by weight of 4- (3, 5-dimethylpyridin-4-yl) phenyltrifluoroacetate was replaced with 0.5% by weight of 4- (3, 5-dimethylpyridin-4-yl) phenyltrifluoropropionate, and a lithium ion battery nonaqueous electrolytic solution C2 and a button cell S2 were prepared.
Example 3
Preparation of the first additive:
dissolving 3, 5-dimethyl-4-bromopyridine, 4- (trimethylacetate) phenylboronic acid and tetrakis (triphenylphosphine) palladium in toluene, uniformly mixing, then adding a sodium carbonate aqueous solution (2.0mol/L), and refluxing for 24 hours under the protection of argon (inert gas), wherein the reaction temperature is 120 ℃. After the reaction is finished, the mixture solution is cooled to room temperature, ethyl acetate is used for extraction, an organic phase is dried by anhydrous magnesium sulfate, a crude product is obtained after the solvent is dried by spinning, and the pure product of the 4- (3, 5-dimethylpyridine-4-yl) phenyl trimethyl acetate is obtained through column chromatography separation. The structural formula is as follows:
nonaqueous electrolyte and button cells were prepared by the same procedure as in example 1, except that: in the step (2), the lithium ion battery non-aqueous electrolyte C3 and the button cell S3 are prepared by replacing 0.1% by weight of 4- (3, 5-dimethylpyridin-4-yl) phenyl trifluoroacetate with 1% by weight of 4- (3, 5-dimethylpyridin-4-yl) phenyl trimethylacetate.
Example 4
Preparation of the first additive:
3, 5-dimethyl-4-bromopyridine, 4- (trifluoroacetic acid methyl ester group) phenylboronic acid and tetrakis (triphenylphosphine) palladium are dissolved in toluene, mixed uniformly, and then added with a sodium carbonate aqueous solution (2.0mol/L) and refluxed for 24 hours under the protection of argon (inert gas), wherein the reaction temperature is 120 ℃. After the reaction is finished, cooling the mixture solution to room temperature, extracting with ethyl acetate, drying an organic phase with anhydrous magnesium sulfate, spin-drying a solvent to obtain a crude product, and separating by column chromatography to obtain a pure product of 4- (3, 5-dimethylpyridine-4-yl) benzyl trifluoroacetate, wherein the structural formula of the product is as follows:
nonaqueous electrolyte and button cells were prepared by the same procedure as in example 1, except that: in the step (1), 5 weight percent of 4- (3, 5-dimethylpyridin-4-yl) benzyltrifluoroacetate is used for replacing 0.1 weight percent of 4- (3, 5-dimethylpyridin-4-yl) phenyltrifluoroacetate, and a lithium ion battery non-aqueous electrolyte C4 and a button cell S4 are prepared.
Example 5
Preparation of the first additive:
3, 5-dimethyl-4-bromopyridine, 4- (trifluoro-methyl propionate) phenylboronic acid and tetrakis (triphenyl phosphorus) palladium are dissolved in toluene, and after uniform mixing, an aqueous solution of sodium carbonate (2.0mol/L) is added and refluxed for 24 hours under the protection of argon (inert gas), and the reaction temperature is 120 ℃. After the reaction is finished, cooling the mixture solution to room temperature, extracting with ethyl acetate, drying an organic phase with anhydrous magnesium sulfate, spin-drying a solvent to obtain a crude product, and separating by column chromatography to obtain a pure product of 4- (3, 5-dimethylpyridine-4-yl) benzyl trifluoropropionate, wherein the structural formula of the pure product is as follows:
nonaqueous electrolyte and button cells were prepared by the same procedure as in example 1, except that: and (2) adding 7% of 4- (3, 5-dimethylpyridin-4-yl) benzyl trifluoropropionate instead of 0.1% of 4- (3, 5-dimethylpyridin-4-yl) phenyl trifluoroacetate by weight in the step (1) to prepare a lithium ion battery non-aqueous electrolyte C5 and a button cell S5.
Comparative example 1
Nonaqueous electrolyte and button cells were prepared by the same procedure as in example 1, except that: and (2) preparing a lithium ion battery non-aqueous electrolyte DC1 and a button cell DS1 without using an ester additive containing pyridine in the step (1).
Performance testing
(1) Testing of battery charging and discharging performance
Each of the experimental button cells S1 to S5 and DS1 was discharged to 0.005V at a constant current of 0.1mA at room temperature, then charged to 1.5V at a constant current of 0.1mA, the discharge capacity and the charge capacity of the cell were recorded, and the charge-discharge efficiency (%) -charge capacity/discharge capacity × 100% was calculated. The test results are shown in table 1.
TABLE 1
(2) Battery cycling test
Charging the battery to 4.95V at constant current and constant voltage with 1C multiplying power (about 0.5mA) at normal temperature, stopping the charging with 0.05mA, then discharging to 3.0V with 0.5mA constant current, recording the first charging capacity and discharging capacity, and calculating the discharging efficiency (%); after the charge and discharge cycles were repeated 100 times in this manner, the discharge capacity at the 100 th cycle was recorded, and the capacity retention (%) after the cycles was calculated as discharge capacity at 100 cycles/first discharge capacity × 100%; the cut-off voltage was 4.95V. The test results are shown in table 2.
As can be seen from tables 1 and 2, the effect of the first additive of the present invention is apparent, the battery prepared using the above electrolyte has good charge and discharge performance test and cycle test, and the battery can be applied at a high voltage of 4.95V.
TABLE 2
Claims (10)
1. A nonaqueous electrolyte solution, comprising a lithium salt, a first organic solvent, and a first additive, wherein the first additive has the following structural formula:
wherein, R1, R2, R3 and R4 are respectively and independently selected from one of hydrogen atom, alkyl, halogenated alkyl, alkoxy and halogen atom; r5 is selected from one of alkyl, haloalkoxy, phenyl and halophenyl; wherein the halogen is F, Cl, Br and I; n is 0 to 5 and is an integer.
2. The nonaqueous electrolytic solution of claim 1, wherein R1, R2, R3 and R4 are each independently selected from an alkyl group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms; r5 is one selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, a haloalkoxy group having 1 to 5 carbon atoms, a phenyl group and a halophenyl group.
3. The nonaqueous electrolytic solution of claim 1, wherein the first additive is one or more of 4- (3, 5-dimethylpyridin-4-yl) phenyltrifluoroacetate, 4- (3, 5-dimethylpyridin-4-yl) phenyltrifluoropropionate, 4- (3, 5-dimethylpyridin-4-yl) phenyltrimethyiacetate, 4- (3, 5-dimethylpyridin-4-yl) benzyltrifluoroacetate, and 4- (3, 5-dimethylpyridin-4-yl) benzyltrifluoropropionate.
4. The nonaqueous electrolytic solution of claim 1, wherein the additive is contained in an amount of 0.1% to 10% based on the total mass of the nonaqueous electrolytic solution.
5. The nonaqueous electrolytic solution of claim 1, further comprising a second additive, wherein the second additive comprises one or more of 1,3 propane sultone, 1,4 butane sultone, propenyl-1, 3-sultone, vinyl sulfate, propylene sulfate, butylene sulfite, vinylene carbonate, fluoroethylene carbonate, lithium bis (fluorosulfonyl) imide and lithium bis (fluorosulfonyl) imide.
6. The nonaqueous electrolytic solution of claim 5, wherein the content of the second additive is 0.05% to 20% based on the total mass of the nonaqueous electrolytic solution.
7. The nonaqueous electrolytic solution of claim 1, wherein the first organic solvent is one or more selected from dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, dipropyl carbonate, ethylene carbonate, propylene carbonate, vinylene carbonate, gamma-butyrolactone, sultone, ethylene sulfite, propylene sulfite, methyl sulfide, diethyl sulfite, methyl formate, methyl acrylate, methyl butyrate and ethyl acetate.
8. The nonaqueous electrolytic solution of claim 1, wherein the lithium salt is one or more selected from the group consisting of LiBOB, LiPF6, LiBF4, LiSbF6, LiClO4, LiCF3SO3, Li (CF3SO2)2N, LiC4F9SO3, LiAlO4, LiAsF6, LiAlCl4, LiCl, LiI, and lithium carbonate low in fatty acid, and the concentration of the lithium salt is 0.3 to 3 mol/L.
9. A battery comprising a battery case, and a cell and a nonaqueous electrolytic solution sealed in the battery case, the cell comprising a positive electrode, a negative electrode and a separator, wherein the nonaqueous electrolytic solution is the nonaqueous electrolytic solution according to any one of claims 1 to 8.
10. A vehicle incorporating the battery of claim 9.
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