CN114122493B - Nonaqueous electrolyte for lithium ion battery and lithium ion battery - Google Patents

Nonaqueous electrolyte for lithium ion battery and lithium ion battery Download PDF

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CN114122493B
CN114122493B CN202010899847.3A CN202010899847A CN114122493B CN 114122493 B CN114122493 B CN 114122493B CN 202010899847 A CN202010899847 A CN 202010899847A CN 114122493 B CN114122493 B CN 114122493B
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ion battery
lithium ion
carbonate
compound
nonaqueous electrolyte
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CN114122493A (en
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钱韫娴
胡时光
褚艳丽
康媛媛
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Shenzhen Capchem Technology 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
    • H01M10/052—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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-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
    • H01M10/42—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
    • 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
    • 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

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

The invention relates to the technical field of lithium ion battery electrolyte, and discloses a lithium ion battery nonaqueous electrolyte and a lithium ion battery prepared from the same. When the lithium ion battery nonaqueous electrolyte provided by the invention is used for further preparing the lithium ion battery, the high-temperature storage and high-temperature cycle performance of the battery can be improved at the same time, and the thickness expansion rate of the battery in storage can be effectively reduced.

Description

Nonaqueous electrolyte for lithium ion battery and lithium ion battery
Technical Field
The invention relates to the technical field of lithium ion battery electrolyte, in particular to a lithium ion battery nonaqueous electrolyte and a lithium ion battery.
Background
Lithium ion batteries have been developed in the field of portable electronic products due to a series of advantages of high operating voltage, high safety, long life, no memory effect, and the like. With the development of new energy automobiles, the lithium ion battery has a huge application prospect in a power supply system for the new energy automobiles.
As the blood of the lithium ion battery, the electrolyte plays a vital role in improving the energy density, the cycle stability and the like of the lithium ion battery. In the charge and discharge process of the lithium ion battery, a series of reactions occur between the electrolyte and the electrode material along with the reversible intercalation/deintercalation reaction of Li +, so that a solid electrolyte interface film (SEI film) is formed to cover the surface of the electrode material. As an electronic insulator and a lithium ion conductor, the stable SEI film can prevent the electrolyte from further contacting with an electrode material, and has a great influence on electrochemical performance and safety performance of a lithium ion battery. On the contrary, the unstable SEI film can cause continuous consumption and continuous reaction of electrolyte to generate a series of irreversible byproducts, so that the internal resistance of the battery is increased, the volume of the battery is expanded, even fire or explosion can be caused in serious cases, and great hidden danger is caused to the safety of the battery. Therefore, the stability of the SEI film may determine the performance of the lithium ion battery.
Optimizing the composition of the electrolyte is an important method for improving the SEI film stability of the lithium ion battery, and compared with the organic solvent and lithium salt, the SEI film has the advantages of small additive demand amount, remarkable effect and lower cost, so that a plurality of scientific researchers select to use different film forming additives (such as vinylene carbonate, fluoroethylene carbonate and ethylene carbonate) to improve various performances of the battery. The Aurbach et al study the additive Vinylene Carbonate (VC) by electrochemical and spectroscopic methods, and found that VC can improve the cycle performance of the battery, especially at high temperatures, and reduce the irreversible capacity. The main reason for this is that VC can polymerize on the graphite surface to form a polyalkyllithium carbonate film, thereby inhibiting the reduction of solvents and salt anions. 5% by volume of Ethylene Sulfite (ES) or Propylene Sulfite (PS) is added to 1mol/L LiClO 4/PC by G.H.Wrodnagg et al, which can effectively prevent PC molecules from being embedded into graphite electrodes and can improve the low-temperature performance of the electrolyte. The reason for this may be that the reduction potential of ES is about 2V (vs. Li/Li +), and the SEI film can be formed on the surface of the graphite anode in preference to the solvent reduction.
Although the above-mentioned studies have played a very important role in improving the battery performance, up to now, the research work has not been mature enough, for example, reports about additives for improving the operating temperature range of lithium ion batteries are not very large, and especially, the types of additives for improving the high temperature performance of lithium ion batteries are very limited.
Disclosure of Invention
The invention aims to solve the problem of poor performance of a lithium ion battery at high temperature in the prior art, and provides a non-aqueous electrolyte of the lithium ion battery and the lithium ion battery prepared by adopting the electrolyte, wherein the battery prepared by adopting the electrolyte can simultaneously improve the high-temperature storage and high-temperature cycle performance of the battery.
In order to achieve the above object, a first aspect of the present invention provides a nonaqueous electrolytic solution for a lithium ion battery,
The nonaqueous electrolytic solution contains an organic solvent, a lithium salt, and a compound represented by the following formula (1) and/or formula (2):
In formulas (1) and (2), R 1-R6 is each independently selected from hydrogen, alkyl or haloalkyl of 1 to 6 carbon atoms, ether or halogenated ether of 1 to 8 carbon atoms, unsaturated hydrocarbon of 2 to 6 carbon atoms, or ester of 1 to 6 carbon atoms.
Preferably, the alkyl group of 1 to 6 carbon atoms is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, neobutyl or tert-butyl.
Preferably, the haloalkyl group of 1 to 6 carbon atoms is selected from haloalkyl groups of 1 to 6 carbon atoms in which at least one hydrogen in the alkyl group is substituted with a halogen element; more preferably, the halogen element is fluorine.
Preferably, the unsaturated hydrocarbon group of 2 to 6 carbon atoms is selected from vinyl, propenyl, allyl, propynyl, propargyl, methylvinyl or methallyl.
Preferably, the compound represented by the formula (1) is selected from one or more of the compounds having the following structures:
compound 7, Compound 8,Compound 9,Compound 10,Compound 11Compound 12.
Preferably, the compound represented by the formula (2) is selected from one or more of the compounds having the following structures:
Compound 1,
Compound 2,Compound 3,
Compound 4,
Compound 5,
Compound 6.
Preferably, the content of the compound represented by the formula (1) is 10ppm or more of the total weight of the lithium ion battery nonaqueous electrolyte; more preferably, the content of the compound represented by the formula (1) is 10ppm to 3% by weight based on the total weight of the nonaqueous electrolyte solution for lithium ion batteries.
Preferably, the content of the compound represented by the formula (2) is 10ppm to 1 wt% based on the total weight of the nonaqueous electrolyte solution for lithium ion batteries; more preferably, the content of the compound represented by the formula (2) is 10ppm to 0.8% by weight based on the total weight of the nonaqueous electrolyte solution for lithium ion batteries.
Preferably, the organic solvent is a mixture of cyclic carbonates and chain carbonates.
Preferably, the cyclic carbonate is selected from one or more of ethylene carbonate, propylene carbonate, butylene carbonate and butylene carbonate.
Preferably, the chain carbonate is selected from one or more of dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate and propylmethyl carbonate.
Preferably, the lithium salt is selected from one or more of LiPF6、LiBF4、LiPO2F2、LiTFSI、LiBOB、LiDFOB、LiSbF6、LiAsF6、LiN(SO2CF3)2、LiC(SO2CF3)3 and LiN (SO 2F)2).
Preferably, the content of the lithium salt in the nonaqueous electrolyte of the lithium ion battery is 0.5-3mol/L; more preferably, the content of the lithium salt in the lithium ion battery nonaqueous electrolyte is 0.7-1.5mol/L.
Preferably, the lithium salt is selected from LiPF 6 and/or LiPO 2F2.
Preferably, the nonaqueous electrolytic solution further comprises an additive selected from one or more of unsaturated cyclic carbonates, fluorinated cyclic carbonates, cyclic sultones and cyclic sulfates.
Preferably, the unsaturated cyclic carbonate is selected from one or more of vinylene carbonate, ethylene carbonate and methylene ethylene carbonate.
Preferably, the fluorinated cyclic carbonate is selected from one or more of fluoroethylene carbonate, trifluoromethyl ethylene carbonate and bis fluoroethylene carbonate.
Preferably, the cyclic sultone is selected from one or more of 1, 3-propane sultone, 1, 4-butane sultone and propenyl-1, 3-sultone.
Preferably, the cyclic sulfate is selected from the group consisting of vinyl sulfate, vinyl 4-methylsulfate andOne or more of the following.
More preferably, the additive is vinylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone,And one or more of vinyl sulfate.
Preferably, the content of the additive is 0.1-5 wt% of the total weight of the lithium ion battery non-aqueous electrolyte.
The second aspect of the invention provides a lithium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm arranged between the positive electrode and the negative electrode, and the nonaqueous electrolyte of the lithium ion battery in the first aspect of the invention.
Preferably, the active material of the positive electrode of the lithium ion battery is selected from one or more of LiNixCoyMzL(1-x-y-z)O2、LiCox'L(1-x')O2、LiNix"L'y'M(2-x"-y')O4 and Li z'MPO4,
Wherein L is one or more of Al, sr, mg, ti, ca, zr, zn, si and Fe;
l' is one or more of Co, al, sr, mg, ti, ca, zr, zn, si and Fe;
m is one or more of Fe, al, mn and Co;
and x is more than or equal to 0 and less than or equal to 1,0 y is less than or equal to 1, and 0 is less than or equal to 1 y is less than or equal to 1,0 to less than or equal to 'is less than or equal to 1,0.3 is less than or equal to x' less than or equal to 0.6 and less than or equal to 0.01 less than or equal to 0.6 and 0.01 is less than or equal to.
Through the technical scheme, when the non-aqueous electrolyte of the lithium ion battery is adopted and the lithium ion battery is further prepared, the capacity retention rate of the lithium ion battery during storage and use at high temperature can be remarkably improved, and the thickness expansion rate of the battery during storage can be effectively reduced.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a lithium ion battery nonaqueous electrolytic solution comprising an organic solvent, a lithium salt, and a compound represented by the following formula (1) and/or formula (2):
In formulas (1) and (2), R 1-R6 is each independently selected from hydrogen, alkyl or haloalkyl of 1 to 6 carbon atoms, ether or halogenated ether of 1 to 8 carbon atoms, unsaturated hydrocarbon of 2 to 6 carbon atoms, or ester of 1 to 6 carbon atoms.
According to the invention, preferably, the alkyl group of 1 to 6 carbon atoms is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, neobutyl or tert-butyl.
Preferably, the haloalkyl group of 1 to 6 carbon atoms is selected from haloalkyl groups of 1 to 6 carbon atoms in which at least one hydrogen in the alkyl group is substituted with a halogen element; more preferably, the halogen element is fluorine.
Preferably, the unsaturated hydrocarbon group of 2 to 6 carbon atoms is selected from vinyl, propenyl, allyl, propynyl, propargyl, methylvinyl or methallyl.
According to the present invention, preferably, the compound represented by the formula (1) is selected from one or more of compounds having the following structures:
compound 7,
Compound 8,Compound 9,Compound 10,Compound 11Compound 12.
According to the present invention, preferably, the compound represented by the formula (1) is selected from one or more of compounds having the following structures:
Compound 1,
Compound 2,Compound 3,
Compound 4,
Compound 5
Compound 6.
In the present invention, the compound represented by the formula (1) may be synthesized according to the following method:
reacting a compound represented by the formula (A) with a compound represented by the formula (B-1) and/or a compound represented by the formula (B-2) in the presence of an acid-binding agent at a temperature of-10 ℃ to 20 ℃ to obtain a compound represented by the formula (1).
Wherein in formula (A) and formula (B), R 1-R4 may each be independently selected from hydrogen, alkyl or haloalkyl of 1 to 6 carbon atoms, ether or halogenated ether of 1 to 8 carbon atoms, unsaturated hydrocarbon of 2 to 6 carbon atoms or ester of 1 to 6 carbon atoms.
Wherein the acid-binding agent may be selected conventionally in the art, for example, may be N, N-Diisopropylethylamine (DIEA), pyridine, triethylamine, etc., and in the present invention, preferably, the acid-binding agent is triethylamine.
The target compound may be obtained after the reaction by a treatment method conventional in the art, and may be obtained by a method such as column chromatography.
In the present invention, the compound represented by the formula (2) may be synthesized according to the following method: firstly, reacting a compound represented by the following formula (C) with thionyl chloride at 30-60 ℃ to obtain a compound represented by the formula (D); then, reacting the compound represented by the formula (D) with the compound represented by the formula (E) at 0-60 ℃ to obtain a compound represented by the formula (F); finally, the compound shown in the formula (F) is catalyzed and reacted with an oxidant at the temperature of minus 10 ℃ to 50 ℃ in the presence of ruthenium trichloride, and then the compound shown in the formula (2) is obtained.
Wherein R 5-R6 may each be independently selected from hydrogen, alkyl or haloalkyl of 1 to 6 carbon atoms, ether or halogenated ether of 1 to 8 carbon atoms, unsaturated hydrocarbon of 2 to 6 carbon atoms or ester of 1 to 6 carbon atoms.
Wherein the oxidizing agent may be a conventional choice in the art, preferably, the oxidizing agent is one or more of sodium periodate, sodium hypochlorite, and calcium hypochlorite.
The inventors of the present invention have conducted intensive studies and found that when the compound represented by the formula (1) and/or the formula (2) is contained in the nonaqueous electrolytic solution of a lithium ion battery, both the high-temperature cycle and the storage performance of the lithium ion battery are significantly improved. This is probably because the compound represented by the formula (1) or (2) can react to form a passivation film on the electrode surface during the first charge, thereby suppressing further decomposition of the solvent molecules. In addition, the passivation film formed by the compound is resistant to high temperature, can not be damaged in the high temperature circulation and storage process, and the compound expressed by the formula (1) or the formula (2) can repair other components in the passivation film damaged due to high temperature, so that the stability of the interface film of the battery at high temperature is ensured, and the high temperature circulation and high temperature storage performance of the battery are improved.
According to the present invention, when used for preparing a nonaqueous electrolytic solution, the content of the compound represented by the formula (1) may be 10ppm or more based on the total weight of the nonaqueous electrolytic solution for a lithium ion battery; preferably, the content of the compound represented by the formula (1) is 10ppm to 3% by weight based on the total weight of the nonaqueous electrolyte solution for lithium ion batteries. The content of the compound represented by the formula (2) may be 10ppm to 1 wt% based on the total weight of the lithium ion battery nonaqueous electrolyte; preferably, the content of the compound represented by the formula (2) is 10ppm to 0.8% by weight based on the total weight of the nonaqueous electrolyte solution for lithium ion batteries.
When the content of the compound represented by the formula (1) and/or the formula (2) is within this range, the storage and cycle properties of the lithium ion battery at high temperatures can be effectively improved. When the content of the compound represented by the formula (1) and/or the formula (2) is below this range, the effect is not sufficiently remarkable although there is also a certain improvement effect; when the content of the compound represented by the formula (1) and/or the formula (2) is higher than this range, storage and cycle performance of the lithium ion battery at high temperature may be adversely affected, probably due to the fact that the higher content of the compound represented by the formula (1) and/or the formula (2) increases the viscosity of the electrolyte after being added, further resulting in an increase in the overall impedance of the battery, thereby reducing storage and cycle performance at high temperature.
In the present invention, the organic solvent in the nonaqueous electrolyte solution of the lithium ion battery may be various organic solvents commonly used in the art for preparing nonaqueous electrolyte solutions, and is not particularly limited, and for example, one or more of cyclic carbonates, chain carbonates, carboxylic acid esters, ethers, and the like may be used as the organic solvent.
According to the present invention, preferably, the organic solvent is a mixture of a cyclic carbonate and a chain carbonate, and when the organic solvent is selected from the group consisting of a mixture of a cyclic carbonate and a chain carbonate, a higher dielectric constant and a lower viscosity can be obtained for the nonaqueous electrolytic solution. More preferably, the cyclic carbonate is selected from one or more of ethylene carbonate, propylene carbonate and butylene carbonate; the chain carbonate is selected from one or more of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and methyl propyl carbonate.
In a particularly preferred embodiment of the present invention, the organic solvent is a mixture of three of Ethylene Carbonate (EC), diethyl carbonate (DEC) and ethylmethyl carbonate (EMC), and the content ratio of the three is 1:1:1, by using the above three compounds in the above-mentioned ratio range as the organic solvent, the nonaqueous electrolytic solution can be made to obtain higher conductivity, which is advantageous for improving the overall performance of the battery.
According to the present invention, the lithium salt in the nonaqueous electrolyte solution for a lithium ion battery may use various lithium salts commonly used in the art for preparing a lithium ion battery, and is not particularly limited, and for example, one or more of LiPF6、LiPO2F2、LiBF4、LiBOB、LiClO4、LiCF3SO3、LiDFOB、LiN(SO2CF3)2、LiN(SO2F)2、LiTFSI and LiDFOB and the like may be selected. In the present invention, preferably, the lithium salt is selected from one or more of LiPF 6、LiBF4、LiPO2F2, liTFSI, liBOB, liDFOB, and LiN (SO 2F)2), more preferably, the lithium salt is selected from LiPF 6 and/or LiPO 2F2 when the above lithium salt is used, the conductivity of the nonaqueous electrolyte can be significantly improved, the performance of the lithium ion battery can be improved, and the production cost can be reduced.
In the present invention, the content of the lithium salt may be a usual content in a lithium ion battery in the art, and is not particularly limited. In the invention, the content of the lithium salt in the non-aqueous electrolyte of the lithium ion battery is 0.5-3mol/L; preferably, the content of the lithium salt in the nonaqueous electrolyte of the lithium ion battery is 0.7-1.5mol/L. When the content of the lithium salt is within this range, it is possible to ensure higher conductivity of the nonaqueous electrolytic solution and excellent overall performance of the battery.
In the present invention, the nonaqueous electrolyte for lithium ion batteries may further contain various additives commonly used in the art for improving the performance of lithium ion batteries, for example, as such additives, in addition to the compounds represented by the above formula (1) and/or formula (2): may be selected from unsaturated cyclic carbonates, fluorinated cyclic carbonates, cyclic sultones, cyclic sulfates, and the like.
In the present invention, preferably, the unsaturated cyclic carbonate is selected from one or more of vinylene carbonate (CAS: 872-36-6), ethylene carbonate (CAS: 4427-96-7) and methylene ethylene carbonate (CAS: 124222-05-5).
In the present invention, preferably, the fluorinated cyclic carbonate is selected from one or more of fluoroethylene carbonate (CAS: 114435-02-8), trifluoromethylcarbonate (CAS: 167951-80-6) and bisfluoroethylene carbonate (CAS: 311810-76-1).
In the present invention, preferably, the cyclic sultone is selected from one or more of 1, 3-propane sultone (CAS: 1120-71-4), 1, 4-butane sultone (CAS: 1633-83-6) and propenyl-1, 3-sultone (CAS: 21806-61-1).
In the present invention, preferably, the cyclic sulfate is selected from the group consisting of vinyl sulfate (CAS: 1072-53-3), vinyl 4-methylsulfate (CAS: 5689-83-8), andOne or more of the following.
In the present invention, more preferably, the additive is Vinylene Carbonate (VC), fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS),And one or more of vinyl sulfate (DTD).
The inventors of the present invention have found that when the above-described additive is further added to a lithium ion battery, it can exert a synergistic effect with the compound represented by formula (1) and/or formula (2), thereby further improving the overall performance of the lithium ion battery.
In addition, in addition to the above-described additives, a second lithium salt may be further added as an additive to improve the performance of the lithium ion battery, for example, in a preferred embodiment of the present invention, a second lithium salt LiN (SO 2F)2 as an additive, and LiN (SO 2F)2 as an additive may be added to further improve the capacity retention rate and the capacity recovery rate of the lithium ion battery).
In the present invention, the content of the additive may be a conventional content of various additives in the art in a lithium ion battery. For example, the additive may be present in an amount of 0.1 to 5 wt% based on the total weight of the lithium ion battery nonaqueous electrolyte; preferably, the content of the additive may be 0.1 to 3 wt% based on the total weight of the lithium ion battery nonaqueous electrolyte; more preferably, the content of the additive may be 0.5 to 1 wt% based on the total weight of the lithium ion battery non-aqueous electrolyte.
The second aspect of the invention provides a lithium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm arranged between the positive electrode and the negative electrode, and the nonaqueous electrolyte of the lithium ion battery in the first aspect of the invention.
According to the present invention, the active material of the positive electrode of the lithium ion battery may be selected from one or more of LiNixCoyMzL(1-x-y-z)O2、LiCox'L(1-x')O2、LiNix"L'y'M(2-x"-y')O4 and Li z'MPO4, wherein L is one or more of Al, sr, mg, ti, ca, zr, zn, si and Fe; l' is one or more of Co, al, sr, mg, ti, ca, zr, zn, si and Fe; m is one or more of Fe, al, mn and Co; and x is more than or equal to 0 and less than or equal to 1,0 y is less than or equal to 1, and 0 is less than or equal to 1 y is less than or equal to 1,0 to less than or equal to 'is less than or equal to 1,0.3 is less than or equal to x' less than or equal to 0.6 and less than or equal to 0.01 less than or equal to 0.6 and 0.01 is less than or equal to.
For example, the active material of the positive electrode of the lithium ion battery may be represented by LiNi xCoyMzL(1-x-y-z)O2, where x may be 0.5, y may be 0.2, z may be 0.3, and m may be Mn, that is, the active material of the positive electrode of the lithium ion battery thus represented is LiNi 0.5Co0.2Mn0.3O2.
According to the present invention, the active material of the negative electrode may be selected from various materials commonly used in the art for negative electrode active materials of lithium ion batteries, and is not particularly limited, and may be, for example, one or more of metallic lithium, graphite-based carbon materials, hard carbon materials, soft carbon materials, silicon-based, tin-based, antimony-based, aluminum-based, transition metal compounds; in the present invention, preferably, the active material of the negative electrode is one or more of artificial graphite, natural graphite, and silicon carbon.
In the present invention, the preparation of the positive electrode and the negative electrode of the lithium ion battery may be performed according to a method commonly used in the art for preparing the positive electrode and the negative electrode of the lithium ion battery, without particular limitation. For example, the active material of the positive and negative electrodes may be mixed with a conductive agent and a binder, and the mixture is dispersed in an organic solvent to prepare a slurry, and then the resulting slurry is coated on a current collector and subjected to drying, spreading, and the like. The conductive agent, the adhesive, the organic solvent, the current collector and the like can be materials and substances commonly used in the field, and are not described herein.
According to the present invention, the separator interposed between the positive electrode and the negative electrode may be various materials commonly used as a separator in the art, and is not particularly limited, and for example, may be one or more of a polyolefin-based separator, a polyamide-based separator, a polysulfone-based separator, a polyphosphazene-based separator, a polyethersulfone-based separator, a polyetheretherketone-based separator, a polyetheramide-based separator, and a polyacrylonitrile-based separator; preferably, the separator is selected from polyolefin-based separators and/or polyacrylonitrile-based separators.
In the invention, the preparation of the lithium ion battery can be carried out by adopting a sandwich method commonly used in the field, for example, a diaphragm is arranged between a positive plate and a negative plate coated with an active material, the whole is coiled, the coiled body is flattened and then is placed into a packaging bag for vacuum baking and drying, so as to obtain a battery cell, and then, electrolyte is injected into the battery cell, and the battery cell is formed after vacuum packaging and standing. This method is conventional in the art and will not be described in detail herein.
The present invention will be described in detail by examples. In the following examples, all materials used were commercially available unless otherwise specified.
In the following examples, the preparation method of the compound represented by the formula (2) represented by the compound 2 is as follows:
Reacting the compound represented by the formula (D-1) with the compound represented by the formula (E-1) at 0-60 ℃ under stirring to obtain a compound represented by the formula (F-1); then, the compound shown in the formula (F-1) and oxidizing agents such as sodium periodate, sodium hypochlorite, calcium hypochlorite and the like are catalyzed by ruthenium trichloride at the temperature of between 10 ℃ below zero and 50 ℃ to obtain the compound 2.
In the following examples, the preparation method of the compound represented by the formula (1) represented by the compound 7 is as follows:
And (3) reacting the compound represented by the formula (A-1) with the compound represented by the formula (B-3) at the temperature of-10 ℃ to 20 ℃ under stirring in the presence of an acid-binding agent triethylamine to obtain a compound 7.
Test example 1: high temperature cycle performance test
The lithium ion batteries prepared in the following examples and comparative examples were placed in an oven at a constant temperature of 45 ℃, charged to 4.4V (LiNi 0.5Co0.2Mn0.3O2/artificial graphite battery) or 4.2V (LiNi 0.8Co0.15Al0.05O2/artificial graphite battery) or 4.48V (LiCoO 2/artificial graphite battery) or 3.65V (LiFePO 4/artificial graphite battery) at a constant current of 1C, charged to a constant voltage of 0.02C, and then discharged to 3.0V (LiNi 0.5Co0.2Mn0.3O2/artificial graphite battery, liNi 0.8Co0.15Al0.05O2/artificial graphite battery, liCoO 2/artificial graphite battery) at a constant current of 1C or discharged to 2.5V (LiFePO 4/artificial graphite battery) at a constant current of 1C, and the discharge capacity of the 1 st and 300 th discharge capacities were recorded for 300 cycles.
The capacity retention for the high temperature cycle was calculated as follows:
Capacity retention = 300 th discharge capacity/1 st discharge capacity x 100%.
Test example 2: high temperature storage performance test
The lithium ion batteries prepared in the following examples and comparative examples were charged to 4.4V (LiNi 0.5Co0.2Mn0.3O2/artificial graphite battery) or 4.2V (LiNi 0.8Co0.15Al0.05O2/artificial graphite battery) or 4.48V (LiCoO 2/artificial graphite battery) or 3.65V (LiFePO 4/artificial graphite battery) at normal temperature with a constant current and constant voltage of 1C, the initial discharge capacity and initial battery thickness of the battery were measured, and then after storage in an environment of 60 ℃ for 30 days, the battery was discharged to 3.0V (LiNi 0.5Co0.2Mn0.3O2/artificial graphite battery, liNi 0.8Co0.15Al0.05O2/artificial graphite battery, liCoO 2/artificial graphite battery) with a constant current and constant current of 1C to 2.5V (LiFePO 4// artificial graphite battery), the holding capacity and recovery capacity of the battery at this time and the thickness of the battery after storage were measured, and the battery capacity holding rate, the capacity recovery rate and the thickness expansion rate were calculated as follows:
battery capacity retention (%) =retention capacity/initial capacity×100%;
battery capacity recovery rate (%) =recovery capacity/initial capacity×100%;
thickness expansion ratio (%) = (cell thickness after storage-initial cell thickness)/initial cell thickness×100%.
Example 1
1) Preparation of non-aqueous electrolyte for lithium ion battery
Mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) according to the weight ratio of EC to DEC to EMC=1:1:1, adding lithium hexafluorophosphate (LiPF 6) to the molar concentration of 1mol/L, and adding 10ppm of compound 1 in the total weight of the nonaqueous electrolyte;
2) Preparation of positive plate
Uniformly mixing a positive electrode active material lithium nickel cobalt manganese oxide LiNi 0.5Co0.2Mn0.3O2, conductive carbon black Super-P as a conductive agent and polyvinylidene fluoride (PVDF) as a binder according to the weight ratio of 93:4:3, and dispersing the obtained mixture in N-methyl-2-pyrrolidone (NMP) to obtain positive electrode slurry; and uniformly coating the positive electrode slurry on two sides of an aluminum foil, drying, calendaring and vacuum drying, and welding an aluminum outgoing line by using an ultrasonic welder to obtain a positive electrode plate, wherein the thickness of the positive electrode plate is 120-150 mu m.
3) Preparation of negative plate
Uniformly mixing negative electrode active material artificial graphite, conductive carbon black Super-P as a conductive agent, and Styrene Butadiene Rubber (SBR) as a binder and carboxymethyl cellulose (CMC) according to the weight ratio of 94:1:2.5:2.5, and dispersing the mixture in deionized water to obtain negative electrode slurry; coating the negative electrode slurry on two sides of a copper foil, drying, calendaring and vacuum drying, and welding a nickel outgoing line by an ultrasonic welding machine to obtain a negative plate, wherein the thickness of the negative plate is 120-150 mu m.
4) Preparation of the cell
And placing a three-layer isolating film with the thickness of 20 mu m between the positive plate and the negative plate, winding a sandwich structure formed by the positive plate, the negative plate and the diaphragm, flattening the winding body, putting into an aluminum foil packaging bag, and baking for 48 hours at the temperature of 75 ℃ in vacuum to obtain the battery cell to be injected with the liquid.
5) Injection and formation of battery cell
Injecting the electrolyte prepared in the step 1) into the battery cell prepared in the step 4) in a glove box with the dew point below-40 ℃, and standing for 24 hours after vacuum packaging;
Then the first charge is conventionally formed by the following steps: and (3) carrying out 0.05C constant current charging for 180min,0.2C constant current charging to 3.95V, carrying out secondary vacuum sealing, then further carrying out constant current charging to 4.4V by using the current of 0.2C, and carrying out constant current discharging to 3.0V by using the current of 0.2C after standing for 24hr at normal temperature.
Examples 2 to 29 and comparative examples 1 to 10
The procedure of example 1 was followed, except that the types and the contents of the positive electrode active material of the lithium ion battery, the compound represented by the formula (1) or the formula (2) and the other additives added to the nonaqueous electrolyte were different, as shown in table 1.
In addition, the formation methods of different positive electrode active materials are different, specifically, liNi 0.8Co0.15Al0.05O2/artificial graphite battery: and (3) performing secondary vacuum sealing on the mixture after 0.05C constant current charging 180min,0.1C constant current charging 180min and 0.2C constant current charging 120min, and then further performing constant-voltage charging to 4.2V with a current constant current of 0.2C, stopping the current of 0.05C, and standing at normal temperature for 5min, and discharging to 3V with a constant current of 0.2C.
LiCoO 2/artificial graphite cell: adopting thermocompression, charging with 0.1C constant current for 45min with upper limit voltage of 3.8V, pressure of 8Kg/CC, charging with 0.2C constant current for 30min with upper limit voltage of 4.4V, pressure of 8Kg/CC, charging with 0.5C constant current for 75min with upper limit voltage of 4.4V, pressure of 8Kg/CC, vacuum sealing for the second time, further charging with 0.2C current constant voltage to 4.48V, cutting off current of 0.03C, standing at normal temperature for 5min, and discharging with 0.2C constant current to 3V.
LiFePO 4/artificial graphite cell: the hot-pressing formation is adopted, the upper limit voltage is 3.65V for 120min under the constant current of 0.03C, the pressure is 3Kg/CC, the upper limit voltage is 3.65V for 60min under the constant current of 0.1C, the pressure is 3Kg/CC, the upper limit voltage is 3.65V for 60min under the constant current of 0.2C, the pressure is 6Kg/CC, the secondary vacuum sealing is carried out, then the constant current and the constant voltage are further carried out to 3.65V under the constant current of 0.2C, the cut-off current is 0.05C, and the constant current discharge is carried out to 2.5V under the constant current of 0.2C after the normal temperature is set aside for 5 min.
The properties of the lithium ion batteries prepared in examples 1 to 29 and comparative examples 1 to 10 are shown in Table 1.
TABLE 1
Note that: in table 1/no corresponding substances were added.
From the results of examples 1 to 8 and comparative example 1, it can be seen that when the compound represented by the formula (1) or the formula (2) of the present invention is contained in the nonaqueous electrolyte of the lithium ion battery, the storage and cycle properties of the lithium ion battery at high temperature can be significantly improved as compared with the comparative example in which the above compound is not used.
As is clear from the comparison of the results of examples 4, 9 to 14 and comparative examples 2 to 7, when other additives (vinylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone, etc.) were further added to the nonaqueous electrolyte of the lithium ion battery,And when vinyl sulfate and LiN (SO 2F)2) are used, the cycle and storage performance of the lithium ion battery at high temperature can be further improved.
As can also be seen from table 1, increasing the addition amount of compound 1 (refer to example 1 and example 4) can significantly improve the capacity retention rate and capacity recovery rate of the lithium ion battery, but when the addition amount of compound 1 continues to increase (refer to example 7 and example 8), the performance of the lithium ion battery is instead reduced.
As can be seen from the results of examples 15 to 29 and comparative examples 8 to 10, when the positive electrode active materials of the lithium ion battery are LiNi 0.8Co0.15Al0.05O2、LiCoO2 and LiFePO 4, and the nonaqueous electrolyte contains the compound represented by the formula (1) and/or the formula (2) provided by the present invention, both the high temperature cycle and the storage performance of the obtained lithium ion battery can be significantly improved, except for the positive electrode active material LiNi 0.5Co0.2Mn0.3O2.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (8)

1. A lithium ion battery nonaqueous electrolyte, characterized in that the nonaqueous electrolyte comprises an organic solvent, a lithium salt, and a compound represented by the following formula (1) and/or formula (2):
(1),
(2),
In formulas (1) and (2), each R 1-R6 is independently selected from hydrogen, alkyl or haloalkyl of 1 to 6 carbon atoms, ether or halogenated ether of 1 to 8 carbon atoms, unsaturated hydrocarbon of 2 to 6 carbon atoms, or ester of 1 to 6 carbon atoms;
wherein the content of the compound represented by the formula (1) is 0.5-1 wt% of the total weight of the lithium ion battery nonaqueous electrolyte;
the content of the compound represented by the formula (2) is 50ppm to 0.8 wt% of the total weight of the lithium ion battery nonaqueous electrolyte,
The compound represented by the formula (1) is selected from one or more of the following compounds:
compound 7,
Compound 8,
Compound 9,
Compound 10,
Compound 11
The compound (12) is a compound selected from the group consisting of,
The compound represented by the formula (2) is selected from one or more of the following compounds:
Compound 1,
Compound 2,
Compound 3,
Compound 4,
Compound 5
Compound 6.
2. The lithium ion battery nonaqueous electrolyte according to claim 1, wherein the organic solvent is a mixture of cyclic carbonate and chain carbonate;
the cyclic carbonate is selected from one or more of ethylene carbonate, propylene carbonate, butylene carbonate and butylene carbonate;
the chain carbonate is selected from one or more of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and methyl propyl carbonate.
3. The lithium ion battery nonaqueous electrolyte according to claim 1, wherein the lithium salt is selected from one or more of LiPF6、LiBF4、LiPO2F2、LiTFSI、LiBOB、LiDFOB、LiSbF6、LiAsF6、LiN(SO2CF3)2、LiC(SO2CF3)3 and LiN (SO 2F)2,
The content of the lithium salt in the nonaqueous electrolyte of the lithium ion battery is 0.5-3mol/L.
4. The lithium ion battery nonaqueous electrolyte according to claim 3, wherein,
The lithium salt is selected from LiPF 6 and/or LiPO 2F2;
the content of the lithium salt in the non-aqueous electrolyte of the lithium ion battery is 0.7-1.5mol/L.
5. The lithium ion battery nonaqueous electrolyte according to claim 1, wherein the lithium ion battery nonaqueous electrolyte further comprises an additive,
The additive is one or more selected from unsaturated cyclic carbonate, fluorinated cyclic carbonate, cyclic sultone and cyclic sulfate;
The unsaturated cyclic carbonate is selected from one or more of ethylene carbonate, ethylene carbonate and methylene ethylene carbonate;
The fluorinated cyclic carbonate is selected from one or more of fluoroethylene carbonate, trifluoromethyl ethylene carbonate and bifluorinated ethylene carbonate;
The cyclic sultone is selected from one or more of 1, 3-propane sultone, 1, 4-butane sultone and propenyl-1, 3-sultone;
the cyclic sulfate is selected from the group consisting of vinyl sulfate, vinyl 4-methylsulfate and One or more of the following.
6. The lithium ion battery nonaqueous electrolyte according to claim 5, wherein the additive is vinylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone,And one or more of vinyl sulfate;
The content of the additive is 0.1-5 wt% of the total weight of the lithium ion battery non-aqueous electrolyte.
7. A lithium ion battery comprising a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and the lithium ion battery nonaqueous electrolyte of any one of claims 1 to 6.
8. The lithium-ion battery of claim 7, wherein the active material of the positive electrode of the lithium-ion battery is selected from one or more of LiNixCoyMzL(1-x-y-z)O2、LiCox'L（1-x'）O2、LiNix''L'y'M（2-x''-y'）O4 and Li z'MPO4,
Wherein L is one or more of Al, sr, mg, ti, ca, zr, zn, si and Fe;
l' is one or more of Co, al, sr, mg, ti, ca, zr, zn, si and Fe;
m is one or more of Fe, al, mn and Co;
And x is more than or equal to 0 and less than or equal to 1,0 y is less than or equal to 1, and 0 is less than or equal to 1 y is less than or equal to 1,0 to less than or equal to ' is less than or equal to 1,0.3 is less than or equal to x '.ltoreq.0.6, 0.01 '. 0.6, 0.01.
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