CN112490497A - Non-aqueous electrolyte for lithium ion battery and lithium ion battery using same - Google Patents

Non-aqueous electrolyte for lithium ion battery and lithium ion battery using same Download PDF

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CN112490497A
CN112490497A CN201910858963.8A CN201910858963A CN112490497A CN 112490497 A CN112490497 A CN 112490497A CN 201910858963 A CN201910858963 A CN 201910858963A CN 112490497 A CN112490497 A CN 112490497A
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carbonate
lithium
lithium ion
ion battery
electrolyte
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杨冰
杜建委
吴杰
曹青青
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Shanshan Advanced Materials Quzhou Co ltd
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Shanshan Advanced Materials Quzhou Co ltd
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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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to the field of batteries, and discloses a non-aqueous electrolyte for a lithium ion battery and the lithium ion battery using the same. The non-aqueous electrolyte for the lithium ion battery comprises lithium salt, an organic solvent and an additive, wherein the additive comprises a conventional additive, a lithium sulfonate compound and a nitrile compound, and the conventional additive is selected from fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS), ethylene carbonate (VEC), Vinylene Carbonate (VC), Propylene Carbonate (PC), lithium difluorophosphate (LiPO)2F2) One or more of (a). The sulfur-containing lithium salt additive and the nitrile additive are matched in the electrolyte, so that the normal temperature and high temperature performance of the lithium cobalt oxide battery can be ensured, the low temperature performance of the lithium cobalt oxide battery can be improved, and the performance of the battery caused by the working environment can be reducedAnd (4) limiting.

Description

Non-aqueous electrolyte for lithium ion battery and lithium ion battery using same
Technical Field
The invention relates to the field of batteries, in particular to a non-aqueous electrolyte for a lithium ion battery and the lithium ion battery using the same.
Background
In recent years, lithium ion batteries have attracted much attention, and have been rapidly developed in the fields of mobile phones, digital products, electric vehicles, electric bicycles, electric tools, energy storage, and the like. Compared with other batteries, the lithium ion battery has the advantages of light weight, small volume, high energy density, long cycle life and the like. However, the requirements of digital products such as smart phones and tablet computers on energy density are higher and higher at present, so that commercial lithium ion batteries are difficult to meet the requirements, and the use of a high-energy-density material as the positive electrode of the battery is the most effective way for improving the energy density of the lithium ion battery.
Lithium cobaltate is the first commercialized and large-scale applied anode material in the ion anode material of the monobasic lithium battery, and the working voltage of the lithium cobaltate battery can be increased to more than 4.4V by improving the process. However, as the operating voltage increases, the specific capacity of lithium cobaltate gradually increases, but the cycle performance decreases. Kim in literature (Applied materials)&Interfaces,2014,6,8913-8920) reported that addition of a mono-or bis-nitrile compound to an electrolyte increased LiCoO due to interaction of cyano groups with Co ions2Thermal stability of the battery. However, although the nitrile additive can significantly improve the high-temperature storage and high-temperature cycle performance of the 4.35V high-voltage battery, when the charging voltage of the lithium cobalt oxide lithium ion battery is further improved, the nitrile additive has no significant effect on improving the high-temperature performance of the battery. In addition, the nitrile additive increases the impedance of the lithium cobalt oxide battery and reduces the low-temperature discharge performance of the battery.
Disclosure of Invention
In view of this, the present invention provides a non-aqueous electrolyte for lithium ion batteries, which can stably operate at high voltage, in which a sulfur-containing lithium salt additive and a nitrile additive are used in combination, so as to ensure normal temperature and high temperature performance of lithium cobalt oxide batteries, improve low temperature performance of lithium cobalt oxide batteries, and reduce the limitation of working environment on battery performance.
In order to achieve the purpose of the invention, the non-aqueous electrolyte for the lithium ion battery comprises lithium salt, an organic solvent and an additive, wherein the additive comprises a conventional additive, a lithium sulfonate compound shown as a formula (1) and a nitrile compound shown as a formula (2):
Figure BDA0002199097340000021
in the formula (1), R1Represents an unsaturated hydrocarbon group having 1 to 10 carbon atoms; in the formula (2), R2Represents an alkane, alkene, alkyne, cyclic alkane containing 1 to 10 carbon atoms or a fluoro-product thereof, and n is taken from 0 or 1; the conventional additive is selected from fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS), ethylene carbonate (VEC), Vinylene Carbonate (VC), Propylene Carbonate (PC), lithium difluorophosphate (LiPO)2F2) One or more of (a).
Further, according to some embodiments of the present invention, the lithium sulfonate salt compound represented by formula (1) is selected from one or more of the following compounds:
Figure BDA0002199097340000022
preferably, the lithium sulfonate salt compound represented by the formula (1) accounts for 0.1 to 5%, for example, 0.3 to 0.7% by mass of the electrolyte.
Further, according to some embodiments of the invention, the nitrile compound of formula (2) is selected from one or more of the following compounds:
Figure BDA0002199097340000031
preferably, the nitrile compound represented by the formula (2) accounts for 0.5 to 10%, for example, 0.5 to 1.5% by mass of the electrolyte.
Further, according to some embodiments of the present invention, the conventional additives comprise fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS), and Vinylene Carbonate (VC); preferably, the conventional additive comprises 4.0-6.0% of fluoroethylene carbonate (FEC) by mass of the electrolyte, 3.0-5.0% of 1, 3-Propane Sultone (PS) by mass of the electrolyte and 0.3-0.6% of Vinylene Carbonate (VC) by mass of the electrolyte.
Further onThe lithium salt is selected from LiPF6、LiBF4、LiClO4、LiBOB、LiODFB、LiAsF6、LiN(SO2CF3)2、LiN(SO2F)2One or more of; preferably, the concentration of the lithium salt in the electrolyte is 0.5 to 2M in terms of lithium ions; according to some embodiments of the invention, the concentration of the lithium salt in the electrolyte is 1-1.5M.
Further, the organic solvent comprises one or more of chain carbonate, cyclic carbonate and carboxylic ester; the chain carbonate is selected from one or more of dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC) and dipropyl carbonate (DPC); the cyclic carbonate is selected from one or more of Ethylene Carbonate (EC), Vinylene Carbonate (VC) and Propylene Carbonate (PC); the carboxylic acid ester is selected from one or more of Ethyl Acetate (EA), Ethyl Propionate (EP), Methyl Acetate (MA), propyl acetate (PE), Methyl Propionate (MP), Methyl Butyrate (MB) and Ethyl Butyrate (EB).
Further, the organic solvent comprises Ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC); according to some embodiments of the invention, the Ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) are mixed in a weight ratio of 1:1: 1.
The invention further provides a lithium ion battery, and the lithium ion battery uses the non-aqueous electrolyte for the lithium ion battery.
Preferably, the lithium ion battery is lithium cobaltate (LiCoO)2) Graphite pouch cells, e.g. 4.4V lithium cobaltate (LiCoO)2) A graphite soft package battery.
More preferably, the method for preparing the lithium ion battery comprises the step of injecting the nonaqueous electrolyte for the lithium ion battery into the fully dried 4.4V lithium cobaltate (LiCoO)2) The graphite soft package battery is subjected to the working procedures of laying aside at 45 ℃, forming by a high-temperature clamp and sealing secondarily.
The lithium sulfonate is added into the electrolyte, the permeability of the SEI film to lithium ions is improved due to the addition of the lithium sulfonate, so that the electrolyte has low impedance and good cycle performance, the toughness of the SEI film can be improved due to the existence of unsaturated bonds in the lithium sulfonate, and the high-temperature effect of the lithium sulfonate formed by the sulfonic acid additive is also good. In addition, the lithium sulfonate additive and the nitrile additive are matched for use, so that the normal-temperature and high-temperature performance of the lithium cobalt oxide battery can be guaranteed, the low-temperature performance of the lithium cobalt oxide battery can be improved, and the limitation of the working environment on the battery performance is reduced.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention. It is to be understood that the following description is only illustrative of the present invention and is not to be construed as limiting the present invention.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
The indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular.
Furthermore, the description below of the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily for the same embodiment or example. Further, the technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
Example 1
The non-aqueous electrolyte is prepared by the following method: in a glove box, Ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) were mixed in a weight ratio of 1:1:1, and then lithium hexafluorophosphate was added to dissolve them, to prepare an electrolyte solution having a lithium hexafluorophosphate concentration of 1.1M. Then, Vinylene Carbonate (VC) accounting for 0.5% by mass of the electrolyte, fluoroethylene carbonate (FEC) accounting for 5% by mass of the electrolyte, 1, 3-Propane Sultone (PS) accounting for 4% by mass of the electrolyte, compound (a) accounting for 0.5% by mass of the electrolyte, and compound (4) accounting for 1% by mass of the electrolyte were added to the electrolyte.
The prepared non-aqueous electrolyte for lithium ion battery was injected into a fully dried 4.4V lithium cobaltate (LiCoO)2) Graphite laminate batteryAfter the procedures of standing at 45 ℃, high-temperature jig formation and secondary sealing, the battery performance test was carried out to obtain the battery of example 1.
Example 2
The preparation method of the positive electrode and the negative electrode of the embodiment 2 is the same as that of the embodiment 1; except that the compound (b) was added to the electrolyte in example 2 in an amount of 0.5% by mass of the electrolyte.
Example 3
The preparation method of the positive electrode and the negative electrode of the embodiment 3 is the same as that of the embodiment 1; except that the compound (c) was added to the electrolyte in example 3 in an amount of 0.5% by mass of the electrolyte.
Example 4
The preparation method of the positive electrode and the negative electrode of the embodiment 4 is the same as that of the embodiment 1; except that the compound (d) was added to the electrolyte in example 4 in an amount of 0.5% by mass based on the electrolyte.
Example 5
The preparation method of the positive electrode and the negative electrode of the embodiment 5 is the same as that of the embodiment 1; except that the compound (e) was added to the electrolyte in example 5 in an amount of 0.5% by mass based on the electrolyte.
Example 6
The preparation method of the positive electrode and the negative electrode of the embodiment 6 is the same as that of the embodiment 1; except that the compound (f) was added in an amount of 0.5% by mass based on the electrolyte in example 6.
Example 7
The preparation method of the positive electrode and the negative electrode of example 7 is the same as that of example 1; except that the compound (a) in an amount of 0.5% by mass and the compound (5) in an amount of 1% by mass were added to the electrolyte in example 7.
Example 8
The preparation method of the positive electrode and the negative electrode of the embodiment 8 is the same as that of the embodiment 1; except that the compound (b) in an amount of 0.5% by mass of the electrolyte and the compound (5) in an amount of 1% by mass of the electrolyte were added to the electrolyte in example 8.
Example 9
The preparation method of the positive electrode and the negative electrode of example 9 is the same as that of example 1; except that the compound (c) in an amount of 0.5% by mass of the electrolyte and the compound (5) in an amount of 1% by mass of the electrolyte were added to the electrolyte in example 9.
Example 10
The preparation methods of the positive electrode and the negative electrode of example 10 are the same as those of example 1; except that the compound (d) in an amount of 0.5% by mass of the electrolyte and the compound (5) in an amount of 1% by mass of the electrolyte were added to the electrolyte in example 10.
Example 11
The preparation methods of the positive electrode and the negative electrode of example 11 are the same as those of example 1; except that the compound (e) in an amount of 0.5% by mass and the compound (5) in an amount of 1% by mass were added to the electrolyte in example 11.
Example 12
The preparation methods of the positive electrode and the negative electrode of example 12 are the same as those of example 1; except that the compound (f) in an amount of 0.5% by mass of the electrolyte and the compound (5) in an amount of 1% by mass of the electrolyte were added to the electrolyte in example 12.
Example 13
The preparation methods of the positive electrode and the negative electrode of example 13 are the same as those of example 1; except that the compound (a) in an amount of 0.5% by mass and the compound (19) in an amount of 1% by mass were added to the electrolyte in example 13.
Example 14
The preparation methods of the positive electrode and the negative electrode of example 14 are the same as those of example 1; except that the compound (b) in an amount of 0.5% by mass and the compound (19) in an amount of 1% by mass based on the electrolyte were added to the electrolyte in example 14.
Example 15
The preparation methods of the positive electrode and the negative electrode of example 15 are the same as those of example 1; except that the compound (c) in an amount of 0.5% by mass and the compound (19) in an amount of 1% by mass were added to the electrolyte in example 15.
Example 16
The preparation methods of the positive electrode and the negative electrode of example 16 are the same as those of example 1; except that the compound (d) in an amount of 0.5% by mass and the compound (19) in an amount of 1% by mass were added to the electrolyte in example 16.
Example 17
The preparation methods of the positive electrode and the negative electrode of example 17 are the same as those of example 1; except that the compound (e) in an amount of 0.5% by mass and the compound (19) in an amount of 1% by mass were added to the electrolyte of example 17.
Example 18
The preparation methods of the positive electrode and the negative electrode of example 18 are the same as those of example 1; except that the compound (f) in an amount of 0.5% by mass and the compound (19) in an amount of 1% by mass were added to the electrolyte in example 18.
Example 19
The positive and negative electrodes of example 19 were prepared in the same manner as in example 1; except that the compound (a) in an amount of 0.5% by mass and the compound (21) in an amount of 1% by mass were added to the electrolyte in example 19.
Example 20
The preparation methods of the positive electrode and the negative electrode of example 20 are the same as those of example 1; except that the compound (b) in an amount of 0.5% by mass and the compound (21) in an amount of 1% by mass based on the electrolyte were added to the electrolyte in example 20.
Example 21
The positive and negative electrodes of example 21 were prepared in the same manner as in example 1; except that the compound (c) in an amount of 0.5% by mass of the electrolyte and the compound (21) in an amount of 1% by mass of the electrolyte were added to the electrolyte of example 21.
Example 22
The positive and negative electrodes of example 22 were prepared in the same manner as in example 1; except that the compound (d) in an amount of 0.5% by mass and the compound (21) in an amount of 1% by mass were added to the electrolyte in example 22.
Example 23
The positive and negative electrodes of example 23 were prepared in the same manner as in example 1; except that the compound (e) in an amount of 0.5% by mass and the compound (21) in an amount of 1% by mass based on the electrolyte were added to the electrolyte in example 23.
Example 24
The positive and negative electrodes of example 24 were prepared in the same manner as in example 1; except that in example 24, the compound (f) in an amount of 0.5% by mass of the electrolyte and the compound (21) in an amount of 1% by mass of the electrolyte were added.
Comparative example 1
The non-aqueous electrolyte is prepared by the following method: in a glove box, Ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) were mixed in a weight ratio of 1:1:1, and then lithium hexafluorophosphate was added to dissolve them, to prepare an electrolyte solution having a lithium hexafluorophosphate concentration of 1.1M. Then, Vinylene Carbonate (VC) accounting for 0.5% by mass of the electrolyte, fluoroethylene carbonate (FEC) accounting for 5% by mass of the electrolyte, 1, 3-Propane Sultone (PS) accounting for 4% by mass of the electrolyte, and compound (4) accounting for 1% by mass of the electrolyte were added to the electrolyte.
The prepared non-aqueous electrolyte for lithium ion battery was injected into a fully dried 4.4V lithium cobaltate (LiCoO)2) The battery performance test is carried out on the graphite soft package battery after the procedures of standing at 45 ℃, high-temperature clamp formation and secondary sealing, so as to obtain the battery used in the embodiment 1.
Comparative example 2
The preparation method of the anode and the cathode of the comparative example 2 is the same as that of the comparative example 1; except that the compound (5) was added to the electrolyte of comparative example 2 in an amount of 1% by mass of the electrolyte.
Comparative example 3
The preparation method of the anode and the cathode of the comparative example 3 is the same as that of the comparative example 1; except that the compound (19) was added to the electrolyte of comparative example 3 in an amount of 1% by mass of the electrolyte.
Comparative example 4
The preparation method of the positive electrode and the negative electrode of the comparative example 4 is the same as that of the comparative example 1; except that the compound (21) was added to the electrolyte of comparative example 4 in an amount of 1% by mass of the electrolyte.
The specific electrolyte formulations of each example and comparative example are shown in table 1.
TABLE 1 electrolyte formulations for the examples and comparative examples
Figure BDA0002199097340000101
Figure BDA0002199097340000111
Lithium ion battery performance testing
1. Normal temperature cycle performance
Under the condition of normal temperature (25 ℃), the lithium ion battery is charged to 4.4V under the constant current and the constant voltage of 1C, and then is discharged to 3.0V under the constant current of 1C. After 500 cycles of charge and discharge, capacity retention rate after 500 cycles was calculated:
Figure BDA0002199097340000121
2. high temperature cycle performance
Under the condition of high temperature (45 ℃), the lithium ion battery is charged to 4.4V under the constant current and the constant voltage of 1C, and then is discharged to 3.0V under the constant current of 1C. After 500 cycles of charge and discharge, capacity retention rate after 500 cycles was calculated:
Figure BDA0002199097340000122
3. high temperature storage Properties
The lithium ion battery was subjected to primary 1C/1C charging and discharging (discharge capacity is designated DC) at room temperature (25 ℃ C.)0) Then charging the battery to 4.4V under the condition of 1C constant current and constant voltage; the lithium ion battery is stored in a high-temperature box at 60 ℃ for 1 month, and after being taken out, 1C discharge (the discharge capacity is recorded as DC) is carried out at normal temperature1) (ii) a Then, 1C/1C charging and discharging (discharge capacity is designated as DC) were carried out under ambient conditions2) Calculating the capacity retention rate and the capacity recovery rate of the lithium ion battery by using the following formulas:
Figure BDA0002199097340000123
Figure BDA0002199097340000124
4. low temperature cycle performance
Under the condition of low temperature (0 ℃), the lithium ion battery is charged to 4.4V under the constant current and the constant voltage of 1C, and then is discharged to 3.0V under the constant current of 1C. After 100 cycles of charge and discharge, the capacity retention rate after the 100 th cycle was calculated as:
Figure BDA0002199097340000131
the results of the battery performance tests of the above-described specific examples and comparative examples are shown in table 2.
Table 2 results of performance test of lithium ion batteries of comparative examples and examples
Figure BDA0002199097340000132
Figure BDA0002199097340000141
As can be seen from the test data in the above table, the battery using the nitrile additive alone can exhibit good effects in both normal-temperature cycle and high-temperature cycle, and after 500 cycles at normal temperature (25 ℃) for 1C, the capacity can be maintained at 65% or more, and after 500 cycles at high temperature (C) for 1C, the capacity can be maintained at 60% or more, except for comparative example 1, and after 7 days of storage at high temperature (55 ℃), the battery added with the sulfur-containing lithium salt additive and the battery added with only the nitrile additive have no significant difference in the two performances of capacity retention rate and capacity recovery rate. However, the battery performance of the lithium salt additive containing sulfur is obviously better than that of the battery only added with the nitrile additive on the low-temperature (0 ℃) cycle performance, because the nitrile additive can increase the impedance of the cobalt acid lithium battery and reduce the low-temperature performance of the battery. The sulfur-containing lithium salt additive can increase the permeability of an SEI film formed on the surface of a negative electrode material to lithium ions, thereby reducing the impedance of a battery and improving the low-temperature performance of a lithium cobalt oxide battery. Meanwhile, the existence of unsaturated bonds in the lithium salt additive containing sulfur can increase the toughness of the formed SEI film, and the normal-temperature and high-temperature cycle performance of the battery is improved to a certain extent.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. The non-aqueous electrolyte for the lithium ion battery comprises a lithium salt, an organic solvent and an additive, and is characterized in that the additive comprises a conventional additive, a lithium sulfonate compound shown as a formula (1) and a nitrile compound shown as a formula (2):
Figure FDA0002199097330000011
wherein, in the formula (1), R1Represents an unsaturated hydrocarbon group having 1 to 10 carbon atoms; in the formula (2), R2Represents an alkane, alkene, alkyne, cyclic alkane containing 1 to 10 carbon atoms or a fluoro-product thereof, and n is taken from 0 or 1; the conventional additive is selected from one or more of fluoroethylene carbonate, 1, 3-propane sultone, ethylene carbonate, vinylene carbonate, propylene carbonate and lithium difluorophosphate.
2. The nonaqueous electrolyte solution for a lithium ion battery according to claim 1, wherein the lithium sulfonate salt compound represented by formula (1) is one or more selected from the following compounds:
Figure FDA0002199097330000012
preferably, the lithium sulfonate salt compound represented by the formula (1) accounts for 0.1 to 5%, for example, 0.3 to 0.7% by mass of the electrolyte.
3. The nonaqueous electrolyte solution for a lithium ion battery according to claim 1 or 2, wherein the nitrile compound represented by the formula (2) is one or more selected from the following compounds:
Figure FDA0002199097330000021
preferably, the nitrile compound represented by the formula (2) accounts for 0.5 to 10%, for example, 0.5 to 1.5% by mass of the electrolyte.
4. The nonaqueous electrolyte for a lithium ion battery according to claim 1, wherein the conventional additive comprises fluoroethylene carbonate, 1, 3-propane sultone and vinylene carbonate; preferably, the conventional additive comprises 4.0-6.0% of fluoroethylene carbonate, 3.0-5.0% of 1, 3-propane sultone and 0.3-0.6% of vinylene carbonate based on the electrolyte.
5. The nonaqueous electrolyte solution for lithium ion batteries according to claim 1, wherein the lithium salt is selected from LiPF6、LiBF4、LiClO4、LiBOB、LiODFB、LiAsF6、LiN(SO2CF3)2、LiN(SO2F)2One or more of; preferably, the concentration of the lithium salt in the electrolyte is 0.5 to 2M, for example 1 to 1.5M, in terms of lithium ions.
6. The nonaqueous electrolyte solution for a lithium ion battery according to claim 1, wherein the organic solvent contains one or more of a chain carbonate, a cyclic carbonate, and a carboxylic ester; the chain carbonate is selected from one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and dipropyl carbonate; the cyclic carbonate is selected from one or more of ethylene carbonate, vinylene carbonate and propylene carbonate; the carboxylic ester is selected from one or more of ethyl acetate, ethyl propionate, methyl acetate, propyl acetate, methyl propionate, methyl butyrate and ethyl butyrate.
7. The nonaqueous electrolyte solution for a lithium ion battery according to claim 6, wherein the organic solvent contains ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate; preferably, the ethylene carbonate, diethyl carbonate and ethyl methyl carbonate are mixed in a weight ratio of 1:1: 1.
8. A lithium ion battery using the nonaqueous electrolyte for lithium ion batteries according to any one of claims 1 to 7.
9. The lithium ion battery according to claim 8, wherein the lithium ion battery is a lithium cobaltate/graphite pouch battery, such as a 4.4V lithium cobaltate/graphite pouch battery.
10. The lithium ion battery of claim 8 or 9, wherein the preparation method of the lithium ion battery comprises the steps of injecting the nonaqueous electrolyte for the lithium ion battery of any one of claims 1 to 7 into a fully dried 4.4V lithium cobaltate/graphite soft package battery, and carrying out the procedures of standing at 45 ℃, high-temperature clamp formation and secondary sealing.
CN201910858963.8A 2019-09-11 2019-09-11 Non-aqueous electrolyte for lithium ion battery and lithium ion battery using same Pending CN112490497A (en)

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