CN109193028B - 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 PDFInfo
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- CN109193028B CN109193028B CN201810950718.5A CN201810950718A CN109193028B CN 109193028 B CN109193028 B CN 109193028B CN 201810950718 A CN201810950718 A CN 201810950718A CN 109193028 B CN109193028 B CN 109193028B
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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
- 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
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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
- H01M10/42—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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- 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
- H01M2300/0025—Organic electrolyte
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- 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
Disclosure of the inventionA non-aqueous electrolyte for a lithium ion battery and a lithium ion battery using the same are provided. The non-aqueous electrolyte for the lithium ion battery comprises a lithium salt, an organic solvent and an additive, wherein the lithium salt can be selected from LiPF6、LiBF4、LiClO4And the organic solvent is one or more selected from chain carbonates, cyclic carbonates and carboxylic esters, and can also comprise a nitrile group-containing pyridyl compound shown by a general formula (I) or a nitrile group-containing oxa-pyridopyridine compound shown by a general formula (II). The non-aqueous electrolyte for the lithium ion battery can effectively inhibit metal dissolution, can be complexed with HF in the electrolyte, reduces the content of HF, reduces the corrosion effect of HF on a positive electrode material, and finally improves the cycle life and the capacity retention rate of the battery.
Description
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 non-aqueous electrolyte.
Background
In recent years, the development of lithium ion batteries has attracted much attention, and the lithium ion batteries are rapidly developed in the fields of mobile phone digital code, electric automobiles, electric bicycles, electric tools, energy storage and the like. Due to the increasing demand for endurance, batteries with high energy density have become a hot point of research. On one hand, electrode materials with high energy density, such as high nickel materials, lithium-rich manganese-based electrode materials, silicon-carbon negative electrodes and other electrode materials attract a large amount of eyes; on the other hand, high voltage lithium ion batteries are also the main trend of current research, and present new challenges to battery materials.
Firstly, under the condition of high voltage, metal ions in a high oxidation state are easy to migrate to a negative electrode under the action of an electric field, electrons obtained at the negative electrode become metal to be precipitated, so that the irreversible loss of a positive electrode material is caused, the capacity of a battery is lost, and the cycle life of the battery is shortened. Under the condition of high voltage, active sites on the surface of the anode have high oxidizability, so that the traditional carbonate electrolyte material is oxidized, decomposed and produced gas, and finally potential safety hazards are formed.
Secondly, the most used electrolyte lithium salt of the lithium ion battery is LiPF6It has the advantage of good electrical conductivityRate, wider electrochemical window and better high and low temperature performance; however, LiPF6Have disadvantages of sensitivity to water and thermal instability, and are easily decomposed in the presence of a trace amount of water or at a higher temperature to generate HF, which damages the SEI film and electrode materials, ultimately resulting in a decrease in battery capacity and deterioration in battery performance.
Many solutions to the above problems are available, and SK new technology corporation in patent WO2015088052 mentions that the complexation of the nitrile group of polynitrile compound and high valence metal ions can effectively reduce the dissolution of metal ions and inhibit the oxidative decomposition of electrolyte on the surface of the positive electrode; some traditional film forming additives of the positive electrode, such as benzene and thiophene with a large pi bond structure, unsaturated bond-containing PST and the like, can be polymerized to form a film on the surface of the positive electrode, cover active sites on the surface of the positive electrode, inhibit the oxidative decomposition of electrolyte and the like. To LiPF6By adding dehydration and acid suppression additives such as carbodiimide type additives, etc.
The addition of one additive can solve the corresponding problem, and the solution of various problems requires the matching use of various additives. However, the increase of the additives inevitably introduces more influencing factors, and mutual synergy and side reactions are increased, which may cause damage to other performances of the battery, and the like. The multifunctional additive can simultaneously solve various problems, simplify the electrolyte formula and provide good help for improving the battery performance and improving the controllability.
Disclosure of Invention
The invention aims to overcome the defects of the background technology and provides a non-aqueous electrolyte capable of improving the high-temperature performance and the cycle life of a lithium ion battery and the lithium ion battery using the electrolyte.
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, and has good effects on inhibiting the dissolution of metal ions, reducing the content of HF and protecting a positive electrode material.
Further, the lithium salt may be selected from LiPF6、LiBF4、LiClO4、LiBOB、LiODFB、LiAsF6、LiN(SO2CF3)2、LiN(SO2F)2And the concentration of the lithium salt in the electrolyte is 0.5 to 2M, preferably 1 to 1.5M, in terms of lithium ions.
Further, the organic solvent may be one or more selected from chain carbonates, cyclic carbonates, and carboxylic acid esters.
Still further, the chain carbonate may be selected from one or more of dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), dipropyl carbonate (DPC).
Further, the cyclic carbonate may be selected from one or more of Ethylene Carbonate (EC), Vinylene Carbonate (VC), and Propylene Carbonate (PC).
Further, the carboxylic acid ester may be selected from one or more of Ethyl Acetate (EA), Ethyl Propionate (EP), Methyl Acetate (MA), propyl acetate (PE), Methyl Propionate (MP), Methyl Butyrate (MB), Ethyl Butyrate (EB).
Further, the additive may be one or more selected from fluoroethylene carbonate (FEC), 1,3 Propane Sultone (PS), ethylene carbonate (VEC), and ethylene sulfate (DTD), and preferably, the mass percentage of the additive in the electrolyte is 0.1-15%.
Further, the additive may further comprise a nitrile group-containing pyridine-based compound represented by the general formula (I):
in the general formula (I), X1、X2、X3、X4And X5Each independently represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, a halogen atom, a nitrile group or an alkoxynitrile group of 1 to 5 carbon atoms, and X1、X2、X3、X4And X5In which at least one is a nitrile group or 1-5 carbon atomsAn alkoxynitrile group;
or a nitrile group-containing oxopyridine compound represented by the general formula (II):
in the general formula (II), n has a value of 1 or 2, X1、X2And X3Each independently represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, a halogen atom, a nitrile group or an alkoxynitrile group of 1 to 5 carbon atoms; wherein, X1、X2And X3In the formula (I), at least one is nitrile group or alkoxy nitrile group with 1-5 carbon atoms; r1And R2Represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogen atom.
Preferably, the compound represented by the general formula (I) accounts for 0.5-10% of the electrolyte by mass.
Preferably, the compound represented by the general formula (II) accounts for 0.1-10% of the electrolyte by mass.
Further, according to an embodiment of the present invention, the compound represented by the general formula (I) includes, but is not limited to, the following compounds:
further, the compound (1) -the compound (8) is used in an amount of 0.1 to 10%, for example, 0.5 to 5% by mass based on the electrolyte.
Further, according to an embodiment of the present invention, the compound represented by the general formula (II) includes, but is not limited to, the following compounds:
further, the compound (9) -the compound (13) is used in an amount of 0.1 to 10%, for example, 0.5 to 5% by mass of the electrolyte;
the invention also provides a lithium ion battery which uses the non-aqueous electrolyte for the lithium ion battery, and preferably, the preparation method of the lithium ion battery comprises the steps of injecting the non-aqueous electrolyte for the lithium ion battery into a fully dried 4.35V NCM (nickel: cobalt: manganese ═ 5:2: 3)/graphite soft package battery, standing at 45 ℃, forming by a high-temperature clamp and carrying out secondary sealing.
The non-aqueous electrolyte for the lithium ion battery can effectively inhibit metal dissolution, reduce decomposition and gas production of the electrolyte and inhibit acid to protect the positive electrode. Compared with the traditional lithium ion secondary battery without the additive disclosed by the invention, the electrolyte contains the pyridine compound with nitrile groups, so that a film can be formed on the surface of the positive electrode to cover the active site of the positive electrode, and the nitrile groups can inhibit the dissolution of metal ions through the complexation with the metal ions; and the nitrogen atom on the pyridine ring is rich in electrons and contains lone-pair electrons, so that the nitrogen atom can be complexed with HF in the electrolyte, the content of the HF is reduced, the corrosion of the HF on the anode material is reduced, and the cycle life and the capacity retention rate of the battery are finally improved.
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.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
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.
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.
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), Propylene Carbonate (PC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) were mixed in a weight ratio of 25:5:50:20, and then lithium hexafluorophosphate was added to dissolve them, to prepare an electrolyte solution having a lithium hexafluorophosphate concentration of 1M. Then, 0.5% by mass of vinylene carbonate, 1% by mass of fluoroethylene carbonate (FEC), 1.5% by mass of 1, 3% by mass of lactone of propane sulfonic acid, 1% by mass of lithium difluorophosphate, and 0.3% by mass of the compound (1) were added to the electrolyte.
The prepared nonaqueous electrolyte solution for lithium ion batteries was injected into a fully dried 4.35V NCM (nickel: cobalt: manganese ═ 5:2: 3)/graphite pouch battery, and after the procedures of standing at 45 ℃, high-temperature jig formation, secondary sealing and the like, a battery performance test was performed to obtain the battery used in 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 0.5% of compound (1) was added to the nonaqueous electrolytic solution in example 2 during the preparation.
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 1% of the compound (1) was added to the nonaqueous electrolytic solution in example 3 during the preparation.
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 2% of the compound (1) was added to the nonaqueous electrolytic solution in example 4 during the preparation.
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 3% of the compound (1) was added to the nonaqueous electrolytic solution in example 5 during the preparation.
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 1% of compound (2) was added to the nonaqueous electrolytic solution in example 6 during the preparation.
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 1% of the compound (3) was added to the nonaqueous electrolytic solution in example 7 during the preparation.
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 1% of the compound (4) was added to the nonaqueous electrolytic solution in example 8 during the preparation.
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 1% of compound (5) was added to the nonaqueous electrolytic solution in example 9 during the preparation.
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 1% of the compound (6) was added to the nonaqueous electrolytic solution in example 10 during the preparation.
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 1% of the compound (7) was added to the nonaqueous electrolytic solution in example 11 during the preparation.
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 1% of the compound (8) was added to the nonaqueous electrolytic solution in example 12 during the preparation.
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 1% of the compound (9) was added to the nonaqueous electrolytic solution in example 13 during the preparation.
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 1% of the compound (10) was added to the nonaqueous electrolytic solution in example 14 during the preparation.
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 1% of compound (11) was added to the nonaqueous electrolytic solution in example 15 during the preparation.
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 1% of compound (12) was added to the nonaqueous electrolytic solution in example 16 during the preparation.
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 1% of the compound (13) was added to the nonaqueous electrolytic solution in example 17 during the preparation.
Comparative example 1
The non-aqueous electrolyte is prepared by the following method: in a glove box, Ethylene Carbonate (EC), Propylene Carbonate (PC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) were mixed in a weight ratio of 25:5:50:20, and then lithium hexafluorophosphate was added to dissolve them, to prepare an electrolyte solution having a lithium hexafluorophosphate concentration of 1M. Then, Vinylene Carbonate (VC) was added to the electrolyte in an amount of 0.5% by mass.
The prepared nonaqueous electrolyte for the lithium ion battery was injected into a fully dried 4.35V NCM (nickel: cobalt: manganese ═ 5:2: 3)/graphite pouch battery, and after the procedures of standing at 45 ℃, high-temperature jig formation, secondary sealing and the like, a battery performance test was performed to obtain the battery used in comparative example 1.
Comparative example 2
The non-aqueous electrolyte is prepared by the following method: in a glove box, Ethylene Carbonate (EC), Propylene Carbonate (PC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) were mixed in a weight ratio of 25:5:50:20, and then lithium hexafluorophosphate was added to dissolve them, to prepare an electrolyte solution having a lithium hexafluorophosphate concentration of 1M. Then, 0.5% by mass of vinylene carbonate and 1% by mass of fluoroethylene carbonate (FEC) were added to the electrolyte.
The prepared nonaqueous electrolyte for the lithium ion battery was injected into a fully dried 4.35V NCM (nickel: cobalt: manganese ═ 5:2: 3)/graphite pouch battery, and after the procedures of standing at 45 ℃, high-temperature jig formation, secondary sealing and the like, a battery performance test was performed to obtain the battery used in comparative example 2.
Comparative example 3
The non-aqueous electrolyte is prepared by the following method: in a glove box, Ethylene Carbonate (EC), Propylene Carbonate (PC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) were mixed in a weight ratio of 25:5:50:20, and then lithium hexafluorophosphate was added to dissolve them, to prepare an electrolyte solution having a lithium hexafluorophosphate concentration of 1M. Then, 0.5% by mass of vinylene carbonate, 1% by mass of fluoroethylene carbonate (FEC) and 1.5% by mass of 1, 3% by mass of propane sulfonic acid lactone were added to the electrolyte
The prepared nonaqueous electrolyte for the lithium ion battery was injected into a fully dried 4.35V NCM (nickel: cobalt: manganese ═ 5:2: 3)/graphite pouch battery, and after the procedures of standing at 45 ℃, high-temperature jig formation, secondary sealing and the like, a battery performance test was performed to obtain the battery used in comparative example 3.
The following is a table of electrolyte formulations for each of the examples and comparative examples:
lithium ion battery performance testing
1. Normal temperature cycle performance
Under the condition of normal temperature (25 ℃), the lithium ion battery is charged to 4.2V 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:
2. high temperature cycle performance
Under the condition of high temperature (45 ℃), the lithium ion battery is charged to 4.2V 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:
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, the battery is charged to 4.2V 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:
the cell performance results for each of the above specific examples are shown in the following table:
from the data in the table, when vinylene carbonate (comparative example 1) is added independently and used for a high-potential 4.35V-523/AG soft package battery, normal-temperature cycle, high-temperature cycle performance and 55 ℃ storage performance are poor, the negative electrode of VC mainly forms an organic polymer film, the VC is not high-temperature resistant and is easy to decompose at high temperature, the positive electrode surface can be polymerized into a film, but the heat stability is poor, meanwhile, VC has a low oxidation potential and is easy to oxidize and decompose at high potential, and meanwhile, transition metal ions can play a role in catalytic decomposition; the fluoroethylene carbonate is further added into the comparative example 1 to obtain a comparative example 2, the normal temperature cycle performance of the scheme is obviously improved, but the high temperature cycle performance and the high temperature storage performance are poor, on one hand, VC and FEC cooperatively participate in the formation of an SEI film, the SEI formed at the negative electrode contains an organic polymer film, inorganic LiF and the like, the stability of the film is improved, but the FEC presents the characteristic of instability in a high temperature environment and is easy to defluorinate to form HF, so that the phenomena of deterioration of the high temperature cycle performance and poor high temperature storage performance of the battery are caused. The introduction of 1,3 propane sulfonic acid lactone further improves the normal temperature and high temperature cycle performance of the battery, the corresponding high temperature storage performance is further increased, and the introduction of lithium difluorophosphate mainly improves the normal temperature and high temperature cycle performance and does not obviously improve the high temperature storage performance.
After the additive is adopted, the addition amounts of 0.3%, 0.5%, 1%, 2% and 3% of the compound (1) are respectively added in the embodiments 1 to 4, and the data in the table show that the high-temperature storage performance of the additive is obviously improved after the additive is introduced into the electrolyte; in the case of the normal temperature cycle, when the additive is added in an amount of 1% or less, the cycle performance tends to be improved with the increase in the amount of the additive, and when the additive is added in an amount of 2% or more, the cycle performance is rather deteriorated, so that it can be seen that the optimum amount of the additive is 0.3 to 1%, the effect of improving the high temperature is not obtained when the additive is too small, and the increase in the internal resistance of the battery may be caused when the additive is too large. The influence of the additive on the battery cycle at the high-temperature cycle is similar to that of the additive at the normal temperature, and the introduction of excessive pyridine compounds is unfavorable for the high temperature; comparing the high temperature cycle and storage performance of the nitrile group, fluorine and methyl functional group compounds contained in the pyridine ring, the high temperature performance of the compound introduced with the methyl group is relatively poorer than that of the introduced nitrile group, fluorine atom and oxygen-containing group, which may belong to electron donating group with the methyl group, thereby causing the increase of lone pair electrons on nitrogen in the pyridine and the increase of side reaction, therefore, the pyridine ring of the invention at least contains one electron withdrawing functional group to reduce the electron cloud density on nitrogen, reduce the activity of pyridine and reduce negative effects. The pyridine compound containing nitrile groups is introduced, the nitrile groups in the molecule of the pyridine compound can be polymerized on the surface of the anode to form a film, the activity of the anode is inhibited, the occurrence of side reaction is reduced, and meanwhile, the nitrogen atom in the pyridine molecule has lone pair electrons to play the role of Lewis base, and the pyridine compound can react with a Lewis base under the high-temperature conditionPF produced after decomposition of lithium hexafluorophosphate5Or POF3The compound forms a complex, so that the damage of an acid substance to a battery system is reduced, and the high-temperature performance of the battery is improved. It should be noted that the electron cloud density on nitrogen in pyridine is not too high, and when too high, there is a risk of oxidative decomposition, by introducing unsaturated nitrile group, fluorine atom and oxygen-containing electron-withdrawing group into the molecular structure, lone pair electrons on nitrogen in pyridine can be reduced, thereby reducing the risk of oxidation, when electron-donating methyl group is introduced on pyridine ring, the probability of oxidation of pyridine is enhanced, at this time, in order to ensure the effect of the present invention, an electron-withdrawing group is usually introduced on pyridine ring, thereby reducing the activity of pyridine ring and inhibiting the occurrence of side reaction.
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 (4)
1. A nonaqueous electrolyte for a lithium ion battery, characterized by comprising a lithium salt, an organic solvent and an additive; the lithium salt is LiPF6And the concentration of the lithium salt in the electrolyte is 0.5-2M in terms of lithium ions; the organic solvent is ethylene carbonate, propylene carbonate, ethyl methyl carbonate and diethyl carbonate; the additive comprises vinylene carbonate, fluoroethylene carbonate, 1,3 propane sultone and lithium difluorophosphate, and also comprises a nitrile group-containing pyridyl compound represented by the general formula (I):
in the general formula (I), X1、X2、X3、X4And X5Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, a nitrile groupOr an alkoxynitrile group of 1 to 5 carbon atoms, and X1、X2、X3、X4And X5In the formula (I), at least one is nitrile group or alkoxy nitrile group with 1-5 carbon atoms;
or a nitrile group-containing oxopyridine compound represented by the general formula (II):
in the general formula (II), n has a value of 1 or 2, X1、X2And X3Each independently represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, a halogen atom, a nitrile group or an alkoxynitrile group of 1 to 5 carbon atoms; wherein, X1、X2And X3In the formula (I), at least one is nitrile group or alkoxy nitrile group with 1-5 carbon atoms; r1And R2Represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogen atom.
2. The nonaqueous electrolyte solution for a lithium ion battery according to claim 1, wherein the concentration of the lithium salt in the electrolyte solution is 1 to 1.5M in terms of lithium ions.
3. The nonaqueous electrolyte solution for a lithium ion battery according to claim 1, wherein the compound represented by the general formula (I) accounts for 0.5 to 10% by mass of the electrolyte solution, and the compound represented by the general formula (II) accounts for 0.1 to 10% by mass of the electrolyte solution.
4. A lithium ion battery using the nonaqueous electrolyte for lithium ion batteries according to any one of claims 1 to 3.
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| CN112242559A (en) * | 2019-07-16 | 2021-01-19 | 杉杉新材料（衢州）有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery using same |
| CN111106387B (en) * | 2019-12-30 | 2021-08-17 | 珠海冠宇电池股份有限公司 | Electrolyte and lithium ion battery |
| WO2021174421A1 (en) * | 2020-03-03 | 2021-09-10 | 宁德新能源科技有限公司 | Electrolyte solution and electrochemical device using electrolyte solution |
| CN111244542A (en) * | 2020-03-21 | 2020-06-05 | 湖州安和材料科技有限公司 | Low-temperature-resistant lithium battery electrolyte and preparation process thereof |
| CN116802873A (en) * | 2022-05-25 | 2023-09-22 | 宁德新能源科技有限公司 | Electrochemical device and electronic device comprising same |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011119097A (en) * | 2009-12-02 | 2011-06-16 | Sony Corp | Nonaqueous electrolyte battery |
| CN102709589B (en) * | 2012-02-17 | 2016-04-13 | 深圳新宙邦科技股份有限公司 | Lithium ion battery and electrolyte thereof |
| KR101944009B1 (en) * | 2012-09-19 | 2019-01-30 | 에스케이케미칼 주식회사 | Electrolyte composition for secondary battery and method for producing the same |
| CN103094616A (en) * | 2013-01-30 | 2013-05-08 | 江西优锂新材股份有限公司 | Electrolyte additive, high-voltage electrolyte and lithium ion battery containing electrolyte additive |
| KR102209828B1 (en) * | 2014-07-16 | 2021-01-29 | 삼성에스디아이 주식회사 | Electrolyte additive for lithium battery, electrolyte including the same and lithium battery using the electrolyte |
| CN107210490A (en) * | 2015-02-04 | 2017-09-26 | 3M创新有限公司 | Include lewis acid：The electrochemical cell of lewis base composite electrolyte additive |
| JP6195127B2 (en) * | 2015-04-30 | 2017-09-13 | トヨタ自動車株式会社 | Secondary battery |
| CN107706455A (en) * | 2017-09-20 | 2018-02-16 | 惠州亿纬锂能股份有限公司 | A kind of high voltage multiplying power electrolyte for taking into account high temperature performance and the lithium ion battery using the electrolyte |
| CN107799820A (en) * | 2017-10-24 | 2018-03-13 | 广州天赐高新材料股份有限公司 | Lithium secondary cell electrolyte and its lithium secondary battery |
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