CN110676511A - Lithium ion battery electrolyte and lithium ion secondary battery - Google Patents
Lithium ion battery electrolyte and lithium ion secondary battery 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
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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
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- 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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Abstract
The invention relates to the technical field of lithium ion batteries, and discloses a lithium ion battery electrolyte and a lithium ion secondary battery, wherein the electrolyte contains an organic solvent, a lithium salt and an additive, and the additive contains a silicon cyano sultone compound and at least one substance selected from fluoroethylene carbonate, ethylene sulfate, ethylene sulfite, propylene sulfate, propylene sulfite, 1, 3-propane sultone, adiponitrile, succinonitrile, vinylene carbonate and ethylene carbonate. The lithium ion secondary battery prepared by the lithium ion electrolyte has excellent cycle performance and storage performance at high temperature and high pressure.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery electrolyte and a lithium ion secondary battery containing the same.
Background
The lithium ion battery has the advantages of high voltage, small volume, light weight, high specific energy, no memory effect, no pollution, small self-discharge, long service life and the like, and is widely applied to portable electronic products such as mobile phones, notebooks, digital cameras and the like.
With economic development and technological advancement, environmental and energy issues have become a major concern worldwide. The exhaustion of fossil energy and the development of new energy technology, and the technology of applying lithium ion batteries to automobile power are rapidly developed, which puts higher requirements on the performance of the lithium ion batteries. In order to meet the requirements of long-time operation, high endurance mileage, use in high and low temperature environments, rapid charging and long service life of electric automobiles, lithium ion batteries are required to have higher discharge capacity, energy density, excellent high and low temperature performance and storage performance.
Batteries with high energy density are the hot spot of current research, and increasing the voltage of a lithium ion battery can increase the energy density of the battery, however, with the increase of the voltage of the lithium ion battery, the electrode potential of a positive electrode material is generally increased, which may cause the electrolyte to be oxidized and decomposed at the positive electrode, and seriously affect the cycle life and storage life of the battery.
In addition, high temperature causes an increase in activity of an electrode material inside the battery, side reactions increase, and cycle performance of the battery decreases. In the prior art, researchers adopt a series of methods to modify the surface interface of a material, and improve the cycle performance of an electrode material under high voltage and high temperature by improving the composition, structure and the like of a surface film of the electrode. The modification means comprises modification coating, mechanical grinding, surface film forming and the like on the material, but the methods have complex process, low repeatability and higher cost.
At present, the method for improving the components of the electrolyte by adopting the proper additive is simple to operate and obvious in effect, and is relatively beneficial to industrial application.
However, common additives such as PS and VC have high electrochemical impedance, and cannot give consideration to both the cycle performance and the storage performance of the lithium ion battery at high temperature and high pressure.
Therefore, it is required to develop an electrolyte for a lithium ion battery that has a good balance between battery performance under high voltage and high temperature conditions.
Disclosure of Invention
The invention aims to overcome the defect that the lithium ion battery in the prior art has poor cycle performance and storage performance under high pressure and high temperature.
In order to achieve the above object, in a first aspect, the present invention provides an electrolyte for a lithium ion battery, which contains an organic solvent, a lithium salt, and an additive containing a silacyano sultone compound and at least one selected from fluoroethylene carbonate, ethylene sulfate, ethylene sulfite, propylene sulfate, propylene sulfite, 1, 3-propanesultone, adiponitrile, succinonitrile, vinylene carbonate, and vinylethylene carbonate.
In a second aspect, the present invention provides a lithium ion secondary battery comprising a positive electrode sheet, a negative electrode sheet, a separator, a battery case, and the electrolyte solution of the first aspect of the present invention.
The lithium ion secondary battery prepared by the electrolyte has excellent cycle performance and storage performance at high temperature and high pressure, the capacity retention rate of the battery is 92.02-94.85% under the conditions of 1C cycle and 400 weeks in the environment of 45 ℃, the capacity retention rate is 92.00-94.76% and the capacity recovery rate is 96.20-98.98% after the battery is stored for 30 days in the environment of 60 ℃.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides an electrolyte for a lithium ion battery, which contains an organic solvent, a lithium salt, and an additive containing a silacyano sultone compound and at least one selected from fluoroethylene carbonate, ethylene sulfate, ethylene sulfite, propylene sulfate, propylene sulfite, 1, 3-propanesultone, adiponitrile, succinonitrile, vinylene carbonate, and vinylethylene carbonate.
Preferably, the silicocyano sultone compound has a structure represented by formula (I):
in the formula (I), R1And R2Each independently selected from-H, C1-6Alkyl of (C)1-6Alkoxy of (2), C substituted by 1 to 10 halogens1-6Haloalkyl of (a), C substituted by 1 to 10 halogens1-6Haloalkoxy of (a);
R3and R4Each independently selected from-H, C1-4Alkyl of (C)1-4Or R is3And R4Together form an intra-ring double bond;
n is selected from a positive integer of 1-5;
m is 0 or 1.
In the present invention, C1-6Alkyl groups of (a) include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, and the like.
In the present invention, C1-6Alkoxy groups of (a) include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, cyclopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, cyclobutoxy, n-pentoxy, isopentoxy, neopentoxy, cyclopentoxy, n-hexoxy, isohexoxy, cyclohexyloxy, and the like. E.g. C1-6Alkoxy of is-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH2CH2CH2CH3、-OCH2CH2CH2CH2CH3And the like.
In the present invention, C substituted by 1 to 10 halogens1-6The haloalkyl group of (A) means C1-61 to 10 hydrogen atoms in the alkyl group of (1) are substituted with a halogen atom. The halogen atom is fluorine atom, chlorine atom, bromine atom or iodine atom. For example C substituted by 1 to 10 halogens1-6Haloalkyl of is-CF3、-CH2CF3、-CH2CF2H、-CF2CF3、-CF2CH2CF2H、-CH2CF2CF2H、-CH2CH2CH2Cl、-CH2CH2CH2Br, and the like.
In the present invention, C substituted by 1 to 10 halogens1-6The haloalkoxy group of (A) means C1-61 to 10 hydrogen atoms in the alkoxy group of (a) are substituted with a halogen atom, which is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. For example C substituted by 1 to 10 halogens1-6The haloalkoxy group of (A) is-OCH2F、-OCF3、-OCH2CF3、-OCH2CH2CF3、-OCH2CH2CH2Cl、-OCH2CH2CH2Br, and the like.
In the present invention, C1-4Alkyl groups of (a) include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, cyclobutyl.
In the present invention, C1-4Alkoxy groups of (a) include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, cyclopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, cyclobutoxy.
Further preferably, the silicon cyano sultone compound is at least one of the following compounds:
and in the formula (I1), the formula (I2) and the formula (I3), R1And R2Each independently selected from-H, C1-6Alkyl of (C)1-6Alkoxy of (2), C substituted by 1 to 10 halogens1-6Haloalkyl of (a), C substituted by 1 to 10 halogens1-6N is selected from a positive integer of 1 to 5.
According to a more preferred embodiment, in said formula (I1), said formula (I2) and said formula (I3), R1Is selected from-H, C1-4Alkyl of (C)1-4Alkoxy of (2), C substituted by 1 to 5 halogen1-4Haloalkyl of (a), C substituted by 1 to 5 halogens1-4Halogenoalkoxy of R2Is selected from-H, C1-6Alkyl of (C)1-6Alkoxy of (2), C substituted by 1 to 10 halogens1-6Haloalkyl of (a), C substituted by 1 to 10 halogens1-6N is 1, 2 or 3.
Preferably, the content of the silacyano sultone compound is 0.1-10 wt%, and more preferably 0.5-5 wt% based on the total weight of the electrolyte, and the inventors of the present invention found that when the content of the silacyano sultone compound is limited to 0.5-5 wt%, the lithium ion battery electrolyte of the present invention can further improve the cycle performance and storage performance of a lithium ion battery employing the electrolyte at high temperature and high pressure.
Preferably, the lithium salt is selected from LiPF6、LiClO4、LiBOB、LiBF4、LiPF2O2LiODFB, LiTFSI, LiFSI and LiC (CF)3SO2)3At least one of (1).
Preferably, the concentration of the lithium salt is 0.5 to 2mol/L, and more preferably 0.8 to 1.5 mol/L.
Preferably, the organic solvent is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, propyl propionate, ethyl propionate and butyl propionate.
In the present invention, the organic solvent is more preferably ethylene carbonate, ethyl methyl carbonate, propylene carbonate, and diethyl carbonate in a weight ratio of 30:50:16: 4.
In the invention, the free acid of the electrolyte is less than 20ppm, and the moisture is less than 15 ppm.
As described above, the second aspect of the present invention provides a lithium ion secondary battery comprising a positive electrode sheet, a negative electrode sheet, a separator, a battery case, and the electrolyte solution of the first aspect of the present invention.
The composition and preparation of the electrolyte have been described in detail in the foregoing, and are not described in detail herein.
In the present invention, the positive electrode sheet preferably includes a positive electrode current collector, and a positive electrode active material, a positive electrode binder, and a positive electrode conductive agent for attaching to the positive electrode current collector.
Preferably, in the present invention, the positive electrode active material is selected from LiCoO2、LiMn2O4、LiNixMn2-xO4、LiNixCoyMn1-x-yO2、LiNixCoyAl1-x-yO2At least one of (1).
In LiNixMn2-xO4In (1), x is greater than 0 and less than 2.
In LiNixCoyMn1-x-yO2Wherein x is greater than 0 and less than 1 and y is greater than 0 and less than 1.
In LiNixCoyAl1-x-yO2Wherein x is greater than 0 and less than 1 and y is greater than 0 and less than 1.
Preferably, the content of the positive active material is 90-98 wt% based on the total weight of the positive dry material.
In the present invention, the positive electrode binder includes, but is not limited to, at least one of polytetrafluoroethylene, polyvinylidene fluoride, and styrene butadiene rubber.
Preferably, the content of the positive electrode binder is 0.01-8 wt% based on the total weight of the positive electrode dry material.
In the invention, the positive electrode conductive agent comprises at least one of SP, acetylene black, KS-6 and carbon nano-tubes.
Preferably, the content of the positive electrode conductive agent is 1-8 wt% based on the total weight of the positive electrode dry material.
Preferably, in the present invention, the current collector of the positive electrode is an aluminum foil.
Preferably, in the invention, the positive plate is obtained by dispersing an active material, a conductive agent and a binder in a dispersing agent to prepare a positive slurry, then coating the positive slurry on a current collector and drying to obtain the positive plate, and then rolling, slitting and vacuum high-temperature drying the dried positive plate after punching.
The dispersant used for preparing the positive electrode slurry in the present invention includes, but is not limited to, at least one of N-methylpyrrolidone, N-dimethylformamide, N-diethylformamide, dimethyl sulfoxide, tetrahydrofuran, water, and alcohol dispersants.
Preferably, in the positive electrode slurry, the positive electrode dispersant is used in an amount such that the solid content of the active material in the positive electrode slurry is 40 to 90% by weight, more preferably 50 to 85% by weight. Therefore, the positive electrode slurry can be dispersed more uniformly, and the coating performance is better.
The drying condition of the positive plate is selected according to the type of the adopted dispersant, so that the dispersant in the positive slurry can be removed under the premise of not influencing the performance of the positive plate.
In the present invention, the negative electrode sheet preferably includes a negative electrode current collector, and a negative electrode active material, a negative electrode binder, a negative electrode conductive agent, and a thickener for attaching to the negative electrode current collector.
Preferably, in the present invention, the negative electrode active material is at least one selected from graphite (artificial graphite and/or natural graphite), mesocarbon microbeads, soft carbon, hard carbon, lithium titanate, silicon, and silicon-carbon alloy.
Preferably, the content of the negative active material is 90-98 wt% based on the total weight of the negative dry material.
In the present invention, the negative electrode binder includes, but is not limited to, at least one of styrene-butadiene rubber, polyvinyl alcohol, and polytetrafluoroethylene.
Preferably, the content of the negative electrode binder is 0.1-8 wt% based on the total weight of the negative electrode dry material
In the invention, the negative electrode conductive agent comprises but is not limited to at least one of Super P, acetylene black, KS-6 and carbon nano tube.
Preferably, the content of the negative electrode conductive agent is 0.1-8 wt% based on the total weight of the negative electrode dry material.
Preferably, in the invention, the thickener is sodium carboxymethylcellulose, and the content of the thickener is 0.1-5 wt% based on the total weight of the dry anode material.
In the present invention, the current collector of the negative electrode is preferably a copper foil.
Preferably, in the invention, the negative electrode is obtained by dispersing an active material, a conductive agent, a binder and a thickening agent in a dispersing agent to prepare a negative electrode slurry, then coating the negative electrode slurry on a current collector and drying to obtain a negative electrode sheet, and then rolling, slitting and vacuum high-temperature drying the dried negative electrode sheet after sheet punching.
The dispersant used for preparing the negative electrode slurry in the invention includes, but is not limited to, at least one of N-methylpyrrolidone, N-dimethylformamide, N-diethylformamide, dimethyl sulfoxide, tetrahydrofuran, water and alcohol dispersants.
Preferably, in the anode slurry, the anode dispersant is used in an amount such that the solid content of the active material in the anode slurry is 40 to 90% by weight, more preferably 50 to 85% by weight. Therefore, the cathode slurry is dispersed more uniformly, and has better coating performance.
The drying condition of the negative pole piece is selected according to the type of the adopted dispersant, so that the dispersant in the negative pole slurry can be removed under the premise of not influencing the performance of the pole piece.
In the invention, the diaphragm is arranged between the positive electrode and the negative electrode, and the material of the diaphragm comprises but is not limited to at least one of polypropylene, polyethylene or polyethylene and polypropylene composite diaphragm.
In the present invention, the lithium ion secondary battery includes, but is not limited to, being prepared by the following steps:
s1, manufacturing the lithium ion battery positive plate, the lithium ion battery negative plate and the diaphragm into a battery cell in a lamination mode;
s2, after vacuum baking is carried out on the battery cell prepared in the S1, the battery cell is placed in a battery shell, the electrolyte is injected, and then the battery shell is sealed.
The present invention will be described in detail below by way of examples. In the following examples, cell performance was measured by the following method:
coulombic efficiency (%) - (discharge capacity/charge capacity) × 100%
(1) High-temperature cycle performance test of lithium ion battery
At 45 ℃, charging the lithium ion battery to 4.35V at a constant current of 1C, then charging to 0.05C at a constant voltage of 4.35V, then discharging to 2.75V at a constant current of 1C, and taking the discharge capacity of the lithium ion battery as a cycle, wherein the discharge capacity of the lithium ion battery is the discharge capacity of the first cycle, and the discharge capacity of the lithium ion battery is 100 percent, and the lithium ion battery is subjected to 400-cycle charge/discharge tests according to the method, and the discharge capacity of the 400 th cycle is obtained through detection.
Capacity retention (%) after 400 cycles at 45 ℃ was 400 cycles of discharge capacity/first cycle of discharge capacity × 100%
(2) High-temperature storage performance test of lithium ion battery
Charging the lithium ion battery to 4.35V at a constant current of 1C and then to 0.05C at a constant voltage of 4.35V at room temperature, and after full charge, testing the volume of the lithium ion battery by a drainage method and marking as V0. The cells were then stored at 60 ℃ for 30 days, and the volume of 30 days of storage was recorded as V1.
Thickness expansion ratio (%) (V1/V0) × 100% -1
Charging the lithium ion battery to 4.35V at a constant current of 1C at room temperature, then charging to 0.05C at a constant voltage of 4.35V, recording the charging capacity C0, then discharging to 2.75V at a constant current of 1C, recording the discharging capacity D0, fully charging the battery according to the charging mode, then storing the battery at 60 ℃ for 30 days, after the storage is finished, discharging to 2.75V at a constant current of 1C, recording the discharging capacity D1, then charging to 4.35V at a constant current of 1C, then charging to 0.05C at a constant voltage of 4.35V, and recording the charging capacity C1.
Capacity retention (%) (D1/D0). times.100%
Capacity recovery (%) - (C1/C0). times.100%
Example 1
(1) Preparation of lithium ion battery positive plate
The positive active material nickel cobalt manganese lithium LiNi0.5Co0.2Mn0.3O2Dissolving a conductive agent SP and a binder polyvinylidene fluoride PVDF (polyvinylidene fluoride) in a solvent N-methyl pyrrolidone according to a mass ratio of 96:2:2, uniformly mixing to prepare anode slurry, and uniformly coating the anode slurry on a current collector aluminum foil with a coating amount of 0.040g/cm2And then drying at 120 ℃, performing cold pressing, cutting, slitting and punching, drying for 4h at 85 ℃ under a vacuum condition, and welding tabs to prepare the positive plate of the lithium ion battery meeting the requirements.
(2) Preparation of lithium ion battery negative plate
Dissolving the negative active material artificial graphite, the conductive agent SP, the thickening agent carboxymethylcellulose sodium CMC and the binder styrene butadiene rubber SBR in deionized water according to the mass ratio of 95.5:1:1:2.5, uniformly mixing to prepare negative slurry, and then uniformly coating the negative slurry on a current collector copper foil, wherein the coating weight is 0.020g/cm2And then drying at 85 ℃, performing cold pressing, cutting, slitting and punching, drying for 4h at 110 ℃ under a vacuum condition, and welding a tab to prepare the negative plate of the lithium ion battery meeting the requirement.
(3) Preparation of lithium ion battery electrolyte
LiPF serving as electrolyte of lithium ion battery6Lithium salt with concentration of 1mol/L, and non-aqueous solvent of mixture of ethylene carbonate EC, ethyl methyl carbonate EMC, propylene carbonate PC, diethyl carbonate DEC, wherein EC is EThe weight ratio of MC to PC to DEC was 20:40:16: 4. Adding 1 wt% of
1 weight percent of vinyl sulfate DTD and 1 weight percent of 1, 3-propane sultone PS are evenly stirred to obtain the electrolyte of the lithium ion battery of the embodiment 1.
(4) Preparation of lithium ion battery
And preparing the prepared positive pole piece, negative pole piece and diaphragm into a soft package battery core in a lamination mode, packaging by adopting a polymer, baking for 24 hours at 85 ℃, injecting the prepared electrolyte, and preparing the lithium ion battery with the capacity of 2000mAh through the processes of formation and the like.
The prepared lithium ion secondary battery is subjected to primary charging formation according to the following steps: charging to 3.6V by using a constant current of 0.1C, charging to 3.95V by using a constant current of 0.2C, secondarily vacuum-sealing, charging to 4.35V by using a constant current of 0.2C, standing at normal temperature for 24 hours, and discharging to 3.0V by using a constant current of 0.2C to obtain 4.35V LiNi0.5Co0.2Mn0.3O2Artificial graphite lithium ion secondary battery.
Examples 2 to 18
A lithium ion battery positive electrode, a lithium ion battery negative electrode, an electrolyte and a lithium ion battery were prepared in the same manner as in example 1, except that in the preparation of the lithium ion battery electrolyte in step (3), the structure or the content of the adopted silacyano sultone compound was different, as specifically shown in table 1.
Example 19
The same method as that used in example 3 was used to prepare the positive electrode, the negative electrode, the electrolyte and the lithium ion battery, except that the content of the silacyano sultone compound used in the step (3) of preparing the electrolyte of the lithium ion battery was different, and the content of the silacyano sultone compound used in this example was 0.1 wt%, and the rest was the same as that used in example 3, and specifically shown in table 1.
Example 20
The same method as that used in example 3 was used to prepare the positive electrode, the negative electrode, the electrolyte and the lithium ion battery, except that the content of the silacyano sultone compound used in the step (3) of preparing the electrolyte of the lithium ion battery was different, and the content of the silacyano sultone compound used in this example was 10 wt%, and the rest was the same as that used in example 3, and specifically shown in table 1.
Example 21
The same method as that used in example 3 was used to prepare the positive electrode, negative electrode, electrolyte and lithium ion battery, except that in the step (3) of preparing the electrolyte of the lithium ion battery, the used silicon cyano sultone compound had a different structure, and the rest was the same as that used in example 3, and specifically shown in table 1.
Comparative example 1
A lithium ion battery positive electrode, a negative electrode, an electrolyte and a lithium ion secondary battery were prepared in the same manner as in example 3, except that in the step (3) of preparing the electrolyte of the lithium ion battery, the silicon cyano sultone compound was not added, and the rest was the same as in example 3, specifically as shown in table 1.
Comparative example 2
A lithium ion battery positive electrode, negative electrode, electrolyte and lithium ion secondary battery were prepared in the same manner as in example 3, except that in the preparation of the electrolyte in step (3), 1 wt% of the silacyano sultone compound in example 3 was replaced with LiODFB in an amount of 0.5 wt%, and the remainder was the same as in example 3, specifically as shown in table 1.
Specific parameters of examples 1 to 21 and comparative examples 1 to 2 are shown in Table 1
TABLE 1
The first cycle coulombic efficiency, the high temperature cycle performance and the high temperature storage performance of the lithium ion secondary battery prepared above were tested, and the results are shown in table 2.
TABLE 2
From the results, the lithium ion secondary battery prepared by the lithium ion battery electrolyte has the first cycle coulombic efficiency of 89.00-91.15%, the capacity retention rate of 92.02-94.85% after 1C cycle for 400 weeks at 45 ℃, the capacity retention rate of 92.00-94.76% after 30 days of standing at 60 ℃, the capacity recovery rate of 96.20-98.98% and the thickness expansion rate of 10.30-14.89%; the lithium ion secondary batteries of comparative examples 1-2 had a coulombic efficiency of 85.15-88.25%, a capacity retention of 86.80-88.20% at 45 ℃ after 1C cycle for 400 weeks, a capacity retention of 88.31-90.13% at 60 ℃ after 30 days of storage, a capacity recovery of 91.62-93.33%, and a thickness expansion of 19.40-21.80%.
Therefore, the lithium ion secondary battery prepared by the lithium ion battery electrolyte has excellent cycle performance and storage performance at high temperature and high pressure.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. The electrolyte for the lithium ion battery is characterized by comprising an organic solvent, lithium salt and an additive, wherein the additive comprises a silicon cyano sultone compound and at least one substance selected from fluoroethylene carbonate, ethylene sulfate, ethylene sulfite, propylene sulfate, propylene sulfite, 1, 3-propane sultone, adiponitrile, succinonitrile, vinylene carbonate and ethylene carbonate.
2. The electrolyte of claim 1, wherein the silacyano sultone compound has a structure represented by formula (I):
in the formula (I), R1And R2Each independently selected from-H, C1-6Alkyl of (C)1-6Alkoxy of (2), C substituted by 1 to 10 halogens1-6Haloalkyl of (a), C substituted by 1 to 10 halogens1-6Haloalkoxy of (a);
R3and R4Each independently selected from-H, C1-4Alkyl of (C)1-4Or R is3And R4Together form an intra-ring double bond;
n is selected from a positive integer of 1-5;
m is 0 or 1.
3. The electrolyte of claim 2, wherein the silacyano sultone compound is at least one of:
in the formula (I1), the formula (I2) and the formula (I3), R1And R2Each independently selected from-H, C1-6Alkyl of (C)1-6Alkoxy of (2), C substituted by 1 to 10 halogens1-6Haloalkyl of (a), C substituted by 1 to 10 halogens1-6N is selected from a positive integer of 1 to 5;
preferably, in the formula (I1), the formula (I2) and the formula (I3), R1Is selected from-H, C1-4Alkyl of (C)1-4Alkoxy of (2), C substituted by 1 to 5 halogen1-4Haloalkyl of (a), C substituted by 1 to 5 halogens1-4Haloalkoxy of (a); r2Is selected from-H、C1-6Alkyl of (C)1-6Alkoxy of (2), C substituted by 1 to 10 halogens1-6Haloalkyl of (a), C substituted by 1 to 10 halogens1-6N is 1, 2 or 3.
4. The electrolyte of any of claims 1-3, wherein the silacyano sultone compound is present in an amount of 0.1 to 10 wt.%, based on the total weight of the electrolyte.
5. The electrolyte of claim 4, wherein the silacyano sultone compound is present in an amount of 0.5 to 5 wt% based on the total weight of the electrolyte.
6. The electrolyte of any of claims 1-3, wherein the lithium salt is selected from LiPF6、LiClO4、LiBOB、LiBF4、LiPF2O2LiODFB, LiTFSI, LiFSI and LiC (CF)3SO2)3At least one of (1).
7. The electrolyte of claim 6, wherein the concentration of lithium salt in the electrolyte is 0.5-2 mol/L.
8. The electrolyte of claim 7, wherein the concentration of lithium salt in the electrolyte is 0.8-1.5 mol/L.
9. The electrolyte of any one of claims 1-3, wherein the organic solvent is selected from at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, propyl propionate, ethyl propionate, butyl propionate.
10. A lithium ion secondary battery comprising a positive electrode sheet, a negative electrode sheet, a separator, a battery case, and the electrolyte according to any one of claims 1 to 9.
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| CN201910822959.6A CN110676511A (en) | 2019-09-02 | 2019-09-02 | Lithium ion battery electrolyte and lithium ion secondary battery |
| CN202080061972.5A CN114342143B (en) | 2019-09-02 | 2020-09-02 | Silicon cyano sultone compound, lithium ion battery electrolyte and lithium ion secondary battery |
| PCT/CN2020/113076 WO2021043175A1 (en) | 2019-09-02 | 2020-09-02 | Silylcyano sultone compound, electrolyte solution for lithium ion battery, and lithium ion secondary battery |
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| WO2021043175A1 (en) * | 2019-09-02 | 2021-03-11 | 孚能科技(赣州)股份有限公司 | Silylcyano sultone compound, electrolyte solution for lithium ion battery, and lithium ion secondary battery |
| WO2022050740A1 (en) * | 2020-09-03 | 2022-03-10 | 주식회사 테크늄 | Electrolyte additive for lithium secondary battery, and lithium secondary battery comprising same |
| WO2022203402A1 (en) * | 2021-03-23 | 2022-09-29 | 주식회사 엘지화학 | Compound, nonaqueous electrolytic solution comprising same, and lithium secondary battery |
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| CN114142086A (en) * | 2021-11-16 | 2022-03-04 | 合肥国轩高科动力能源有限公司 | Low-temperature-resistant lithium ion battery electrolyte and lithium ion battery |
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| JP5110625B2 (en) * | 2007-02-02 | 2012-12-26 | パナソニック株式会社 | Electricity storage device |
| WO2011034065A1 (en) * | 2009-09-18 | 2011-03-24 | 三井化学株式会社 | Unsaturated sultone compound, nonaqueous electrolyte solution containing same, and lithium secondary battery |
| CN105428701B (en) * | 2015-12-21 | 2018-02-09 | 东莞新能源科技有限公司 | A kind of electrolyte and the lithium ion battery including the electrolyte |
| CN105481825A (en) * | 2015-12-31 | 2016-04-13 | 石家庄圣泰化工有限公司 | Preparation method of prop-1-ene-1,3-sultone derivatives |
| CN105845982B (en) * | 2016-03-31 | 2018-06-05 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery comprising same |
| WO2018073694A2 (en) * | 2016-10-20 | 2018-04-26 | 3M Innovative Properties Company | Electrolyte solutions and electrochemical cells containing same |
| JP2018156761A (en) * | 2017-03-16 | 2018-10-04 | 三井化学株式会社 | Nonaqueous electrolyte solution for battery, and lithium secondary battery |
| CN108321434A (en) * | 2018-03-23 | 2018-07-24 | 安普瑞斯（无锡）有限公司 | A kind of high-voltage lithium-ion battery electrolyte |
| CN110676511A (en) * | 2019-09-02 | 2020-01-10 | 孚能科技(赣州)股份有限公司 | Lithium ion battery electrolyte and lithium ion secondary battery |
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| WO2021043175A1 (en) * | 2019-09-02 | 2021-03-11 | 孚能科技(赣州)股份有限公司 | Silylcyano sultone compound, electrolyte solution for lithium ion battery, and lithium ion secondary battery |
| WO2022050740A1 (en) * | 2020-09-03 | 2022-03-10 | 주식회사 테크늄 | Electrolyte additive for lithium secondary battery, and lithium secondary battery comprising same |
| WO2022203402A1 (en) * | 2021-03-23 | 2022-09-29 | 주식회사 엘지화학 | Compound, nonaqueous electrolytic solution comprising same, and lithium secondary battery |
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| CN114342143A (en) | 2022-04-12 |
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