CN113506915A - Electrolyte additive, preparation method thereof, electrolyte and lithium ion battery - Google Patents

Electrolyte additive, preparation method thereof, electrolyte and lithium ion battery Download PDF

Info

Publication number
CN113506915A
CN113506915A CN202110800463.6A CN202110800463A CN113506915A CN 113506915 A CN113506915 A CN 113506915A CN 202110800463 A CN202110800463 A CN 202110800463A CN 113506915 A CN113506915 A CN 113506915A
Authority
CN
China
Prior art keywords
electrolyte
additive
reactant
lithium
battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110800463.6A
Other languages
Chinese (zh)
Other versions
CN113506915B (en
Inventor
官向国
钟海敏
周青
朱璐莹
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evergrande New Energy Technology Shenzhen Co Ltd
Original Assignee
Evergrande New Energy Technology Shenzhen Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Evergrande New Energy Technology Shenzhen Co Ltd filed Critical Evergrande New Energy Technology Shenzhen Co Ltd
Priority to CN202110800463.6A priority Critical patent/CN113506915B/en
Publication of CN113506915A publication Critical patent/CN113506915A/en
Application granted granted Critical
Publication of CN113506915B publication Critical patent/CN113506915B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • H01M10/05—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
    • H01M10/42—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

Landscapes

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

Abstract

The invention belongs to the technical field of batteries, and particularly relates to an electrolyte additive and a preparation method thereof, as well as an electrolyte and a lithium ion battery. Wherein, the additive comprises a compound with the structural general formula as shown in the following formula I:
Figure DDA0003164511630000011
formula I; wherein R is1、R2、R3、R4、R5At least one selected from hydrogen, alkyl, alkenyl, alkynyl, alkoxy and halogen. The electrolyte additive has the advantages of flame retardant effect, good high-temperature thermal stability, difficult gas generation, capability of forming a compact SEI film with low impedance and good elasticity on the surface of an electrode, improvement on the normal-temperature/high-temperature cycle performance of a battery, particularly a high-nickel silicon carbon battery, and high performanceTemperature storage performance, and safety performance.

Description

Electrolyte additive, preparation method thereof, electrolyte and lithium ion battery
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to an electrolyte additive and a preparation method thereof, as well as an electrolyte and a lithium ion battery.
Background
The lithium ion battery has the advantages of high specific energy, long cycle life, no memory effect and the like, and is widely applied to the fields of mobile phones, computers, cameras, electric vehicles and the like. With the continuous development of scientific technology, various application fields put higher demands on the performance of the lithium ion battery, wherein the most urgent is to improve the energy density of the lithium ion battery on the premise of ensuring safety. At present, the industry is pursuing higher energy density of lithium batteries, which is also an important index reflecting battery technology. Therefore, a positive electrode material with higher gram capacity is needed to be adopted, and as the selection which can be commercialized at present, the positive electrode is generally made of a high-nickel ternary material, and the negative electrode is made of a silicon-based material. Wherein, the high nickel ternary material has strong oxidizing property to the electrolyte after lithium removal, which causes gas generation of the battery, metal element dissolution and capacity attenuation. And the silicon-based material has huge volume shrinkage in the process of lithium intercalation and deintercalation, so that the SEI film on the surface of the silicon-based material is very easy to crack, and then the repeated growth of the SEI film is generated, and finally, a series of problems of battery impedance increase, flatulence, capacity attenuation and the like are caused. Therefore, the use of the above materials has placed high demands on the electrolyte.
Currently, numerous studies indicate that the cycle performance improvement of the silicon negative electrode is large with fluoroethylene carbonate (FEC). In order to improve the cycle performance of the silicon negative electrode, a high content of FEC is often used as a film forming additive in the existing electrolyte formula to cope with the volume expansion of the silicon negative electrode. However, the FEC is very likely to generate HF at high temperature, thereby continuously accelerating the decomposition of the carbonate electrolyte, and finally causing the battery to be very likely to generate gas at high temperature, which seriously affects the high-temperature cycle performance of the silicon negative electrode battery. Therefore, the stability of the current lithium ion battery electrolyte for high-nickel ternary and other positive electrode materials and silicon-based and other negative electrode materials is still lack of an effective improvement effect, HF and the like are easily generated in the charging and discharging processes, and the safety is poor.
Disclosure of Invention
The invention aims to provide an electrolyte additive, a preparation method thereof, an electrolyte and a lithium ion battery, and aims to solve the problems that the stability defects that gas generation, volume expansion and the like of a positive electrode and a negative electrode in the lithium ion battery are easy to inhibit by the conventional electrolyte to a certain extent, gas is easy to generate in the charging and discharging process, and the safety is poor.
In order to achieve the purpose of the application, the technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides an electrolyte additive comprising a compound having the general structural formula of formula I:
Figure BDA0003164511610000021
formula I; wherein R is1、R2、R3、R4、R5At least one selected from hydrogen, alkyl, alkenyl, alkynyl, alkoxy and halogen.
The compound with the structural general formula I in the electrolyte additive provided by the first aspect of the invention is a terpyridine diphenylphosphine acetylene metal ion complex, wherein a phosphorus-containing group can generate a flame-retardant phosphorus free radical, so that the flame-retardant effect is achieved, and the safety performance of the electrolyte is improved. The compound of the additive formula I general structure has high reduction potential and low oxidation potential, contains groups such as phosphorus-containing groups, alkyl, alkenyl, alkynyl, alkoxy, halogen and the like, can promote the additive to form a compact, low-impedance and good-elasticity SEI film on the surfaces of positive and negative electrodes, cannot crack in the process of lithium intercalation and deintercalation of materials, obviously improves the cycle performance of electrode materials, improves the interface stability of the surfaces of the positive and negative electrode plates, and prevents solvent molecules from reducing on the surface of a negative electrode and oxidizing on the surface of the positive electrode. In addition, the electrolyte additive has good high-temperature thermal stability, is not easy to generate gas under the high-temperature condition, and can improve the normal-temperature/high-temperature cycle performance and the high-temperature storage performance of the battery, particularly the high-nickel silicon carbon battery.
Further, the halogen is selected from at least one of fluorine, chlorine and bromine. Further, the carbon atoms of the alkyl, alkenyl, alkynyl and alkoxy groups are not higher than 6, and the substituents with the carbon atoms higher than 6 can cause the molecular structure of the additive to be too large, thereby causing the viscosity to be too large and reducing the ionic conductivity of the electrolyte. In the additive, alkyl, alkenyl, alkynyl, alkoxy, halogen and other substituents can improve the film forming effect of the additive, improve the solubility of the electrolyte additive to lithium salt and improve the compatibility of the additive and a solvent.
Further, the additives include:
Figure BDA0003164511610000031
Figure BDA0003164511610000032
Figure BDA0003164511610000033
at least one of (1). On one hand, the electrolyte additive can generate phosphorus-containing free radicals, has a flame-retardant effect, and improves the safety performance of the electrolyte. On the other hand, the electrolyte additive has high reduction potential and low oxidation potential, contains groups such as phosphorus-containing groups, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, halogens and the like, is easy to generate electrochemical polymerization reaction on the surface of an electrode to form a compact, low-impedance and good-elasticity SEI film, improves the cycle performance of an electrode material, improves the interface stability of the surfaces of positive and negative pole pieces, prevents solvent molecules from being reduced on the surface of a negative pole and oxidized on the surface of a positive pole, and improves the normal temperature/high temperature cycle performance and high temperature storage performance of a battery, particularly a high-nickel silicon carbon battery.
In a second aspect, the present invention provides a method for preparing an electrolyte additive, comprising the steps of:
mixing and dissolving a reactant A, a reactant B, a catalyst and a first organic solvent, carrying out catalytic reaction, separating to obtain the additive with the structural general formula of the formula I,
Figure BDA0003164511610000041
wherein the structural formula of the reactant A is shown as
Figure BDA0003164511610000042
The structural formula of the reactant B is
Figure BDA0003164511610000043
Wherein R is1、R2、R3、R4、R5Is at least one of hydrogen, alkyl, alkenyl, alkynyl, alkoxy and halogen, and x is halogen.
The preparation method of the electrolyte additive has simple process, is suitable for industrial large-scale production and application, has flame retardant effect, good high-temperature thermal stability, is not easy to generate gas, can form a compact, low-impedance and good-elasticity SEI film on the surface of an electrode, and improves the normal temperature/high temperature cycle performance, high temperature storage performance and safety performance of batteries, particularly high nickel-silicon carbon batteries.
Further, the conditions of the catalytic reaction include: mixing and reacting for 8-24 hours in a dark environment at the temperature of 60-90 ℃; the reactants A and B are fully reacted, the reaction is prevented from being influenced by illumination, and the generation of byproducts is reduced. If the reaction time is too short, the reaction of the reactant A and the reactant B is insufficient.
Further, the molar ratio of the reactant a to the reactant B was 1: (5-10); the method is favorable for full reaction between the reactant A and the catalyst, and if the addition ratio of the reactant A is too high or too low, byproducts are generated, and the yield of the additive is reduced.
Further, in a reaction system obtained by mixing and dissolving the reactant A, the reactant B, the catalyst and the first organic solvent, the mass percentage concentration of the catalyst is 1-10%, and the amount of the catalyst can sufficiently ensure the reaction between the reactant A and the reactant B.
Further, the catalyst is at least one of cuprous iodide, cuprous chloride, cuprous bromide and palladium metal catalyst; these catalysts are all capable of catalyzing the reaction between reactant a and reactant B to form the electrolyte additive.
Further, the first organic solvent is at least one selected from dichloromethane, diisopropylamine, diethylamine, dipropylamine and dibutylamine; the organic solvents have better dissolving effect on the reactant A and the reactant B, so that the reactants are fully dissolved in the organic solvents, full contact reaction between the reactants is facilitated, and an electrolyte additive product is obtained.
Further, the additives include:
Figure BDA0003164511610000051
Figure BDA0003164511610000052
Figure BDA0003164511610000061
the electrolyte additive can generate phosphorus-containing free radicals, has a flame-retardant effect, and improves the safety performance of the electrolyte. The electrode material has high reduction potential and low oxidation potential, contains groups such as phosphorus-containing groups, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, halogens and the like, is easy to generate electrochemical polymerization reaction on the surface of an electrode to form a compact SEI film with low impedance and good elasticity, can not crack in the process of lithium intercalation and deintercalation of the material, remarkably improves the cycle performance of the electrode material, improves the interface stability of the surfaces of positive and negative pole pieces, and prevents the reduction of solvent molecules on the surface of a negative electrode and the oxidation of the surface of a positive electrode. The normal temperature/high temperature cycle performance and high temperature storage performance of the battery, especially the high nickel silicon carbon battery, can be improved.
In a third aspect, the present invention provides an electrolyte comprising a lithium salt, a second organic solvent and the electrolyte additive described above, or the electrolyte additive prepared by the above method.
The electrolyte provided by the third aspect of the invention comprises lithium salt, an organic solvent and the electrolyte additive shown in the structural general formula I, and the additive not only has a flame retardant effect and good high-temperature cycle and storage stability, but also is not easy to generate gas, and an SEI film with good elasticity and low resistance is easily formed on the surface of an electrode, so that the cycle performance of an electrode material can be improved, the high-temperature cycle and storage performance of a battery can be improved, the safety performance of the battery can be improved, and the cycle life of the battery can be prolonged.
Furthermore, in the electrolyte, the mass percentage of the additive is 0.1-10%; the addition amount of the electrolyte enables the electrolyte to have the best flame retardant property, film-forming property and electrochemical comprehensive property.
Further, the mass percentage content of the lithium salt is 10-15%; the lithium salt of this content provides sufficient lithium ions for the electrolyte, ensuring the efficiency of the electrolyte.
Furthermore, the electrolyte also comprises 0.1 to 5 mass percent of auxiliary additive. If the amount of the additive is too large, the film formation resistance is too large and the solubility is lowered; if the amount of the additive is too small, the auxiliary effect is not significant.
Further, the lithium salt is selected from LiCF3SO3、LiC(CF3SO2)3、LiB(C2O4)2、LiF(C2O4)2、LiN(CF3SO2)2At least one of; the lithium salts are easy to dissociate into lithium ions, and the lithium ions are inserted into and taken out of the positive electrode and the negative electrode, so that the cyclic charge and discharge of the battery are realized.
Further, the auxiliary additive is selected from at least one of vinylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone, vinyl sulfate, 1-propylene-1, 3-sultone, ethylene carbonate, tris (trimethylsilane) phosphite, lithium bis-fluorosulfonylimide, lithium difluorophosphate and lithium difluorooxalato borate; the high-temperature stability of the electrolyte is further improved through the auxiliary additives, the film forming effect of the electrolyte on the surface of an electrode is improved, and an electrolyte interphase (SEI) with excellent elasticity is formed on the surface of the electrode, so that the interface reaction on the surface of the electrode is prevented, and the stability and the safety performance of a battery are improved.
Furthermore, the second organic solvent is at least one selected from ethylene carbonate, methyl ethyl carbonate, diethyl carbonate, propylene carbonate, dimethyl carbonate, methyl formate, methyl acetate, methyl propionate, ethyl acetate, propyl propionate, sulfolane, gamma-butyrolactone and dimethyl sulfoxide, and the organic solvents have good compatibility with additives and lithium salts, and are beneficial to the transmission of lithium ions in the charging and discharging processes of the battery.
In a fourth aspect, the present invention provides a lithium ion battery, which includes the above electrolyte.
The lithium ion battery provided by the fourth aspect of the invention can not only improve the flame retardant effect of the lithium ion battery, but also form an elastic SEI film on the surface of the electrode, thereby reducing the gas generation of the battery, improving the cycle performance of the electrode material, improving the interface stability of the surfaces of the positive and negative pole pieces, and preventing the reduction of solvent molecules on the surface of the negative pole and the oxidation of the surface of the positive pole. Therefore, the high-temperature cycle and storage performance of the lithium ion battery are obviously improved, the safety performance of the battery is improved, and the cycle life of the battery is prolonged.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed for the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a reaction flow diagram of a method for preparing an electrolyte additive according to an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the present invention, the term "and/or" describes the association relationship of the associated objects, and means that there may be three relationships, for example, a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present invention, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present invention, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present invention.
The terminology used in the embodiments of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the examples of the invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the mass in the description of the embodiments of the present invention may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the invention. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
The first aspect of the embodiments of the present invention provides an electrolyte additive, which includes a compound having a general structural formula as shown in formula I below,
Figure BDA0003164511610000091
Figure BDA0003164511610000092
formula I; wherein R is1、R2、R3、R4、R5At least one selected from hydrogen, alkyl, alkenyl, alkynyl, alkoxy and halogen.
The compound with the structural general formula I in the electrolyte additive provided by the embodiment of the invention is a terpyridine diphenyl phosphorus acetylene metal ion complex, wherein a phosphorus-containing group can generate a flame-retardant phosphorus free radical, so that the flame-retardant effect is achieved, and the safety performance of the electrolyte is improved. The electrolyte additive disclosed by the embodiment of the invention has high reduction potential and low oxidation potential, contains phosphorus-containing groups, alkyl, alkenyl, alkynyl, alkoxy, halogen and other groups, can promote the additive to form a compact, low-impedance and good-elasticity SEI (solid electrolyte interphase) film on the surfaces of a positive electrode and a negative electrode, cannot crack in the process of lithium intercalation and deintercalation of materials, obviously improves the cycle performance of electrode materials, improves the interface stability of the surfaces of the positive electrode piece and the negative electrode piece, and prevents the reduction of solvent molecules on the surface of the negative electrode and the oxidation of the surface of the positive electrode. In addition, the electrolyte additive has good high-temperature thermal stability, is not easy to generate gas under the high-temperature condition, and can improve the normal-temperature/high-temperature cycle performance and the high-temperature storage performance of the battery, particularly the high-nickel silicon carbon battery.
In the electrolyte additive of the embodiment of the invention, R1、R2、R3、R4、R5The electrolyte additive is at least one selected from hydrogen, alkyl, alkenyl, alkynyl, alkoxy and halogen, wherein the substituent such as alkyl, alkenyl, alkynyl, alkoxy and halogen can improve the film forming effect of the additive, improve the solubility of the electrolyte additive to lithium salt and improve the compatibility of the additive and a solvent. In some embodiments, the halogen is selected from at least one of fluorine, chlorine, bromine. In some embodiments, alkyl, alkenyl, alkynyl, alkoxy groups having not more than 6 carbon atoms, and substituents having more than 6 carbon atoms, may result in the addition ofThe molecular structure of the agent is too large, so that the viscosity is too high, and the ionic conductivity of the electrolyte is reduced.
In some embodiments, the additives comprise:
Figure BDA0003164511610000101
Figure BDA0003164511610000102
at least one of (1). On one hand, the electrolyte additive provided by the embodiment of the invention can generate phosphorus-containing free radicals, has a flame-retardant effect, and improves the safety performance of the electrolyte. On the other hand, the electrolyte additive has high reduction potential and low oxidation potential, contains groups such as phosphorus-containing groups, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, halogens and the like, is easy to generate electrochemical polymerization reaction on the surface of an electrode to form a compact SEI film with low impedance and good elasticity, cannot crack in the process of lithium intercalation and deintercalation of materials, remarkably improves the cycle performance of electrode materials, improves the interface stability of the surfaces of positive and negative pole pieces, and prevents solvent molecules from reducing on the surface of a negative electrode and oxidizing on the surface of a positive electrode. In addition, the additives have good high-temperature thermal stability, are not easy to generate gas under the high-temperature condition, and improve the normal-temperature/high-temperature cycle performance and high-temperature storage performance of the battery, particularly the high-nickel silicon carbon battery.
The electrolyte additive of the embodiment of the present invention can be prepared by the following embodiment method.
As shown in fig. 1, a second aspect of the embodiment of the present invention provides a method for preparing an electrolyte additive, including the steps of:
s10, mixing and dissolving the reactant A, the reactant B, a catalyst and a first organic solvent, carrying out catalytic reaction, separating to obtain the additive with the structural general formula of the formula I,
Figure BDA0003164511610000111
wherein the structural formula of the reactant A is shown as
Figure BDA0003164511610000112
The structural formula of the reactant B is
Figure BDA0003164511610000113
Wherein R is1、R2、R3、R4、R5At least one of hydrogen, alkyl, alkenyl, alkynyl, alkoxy and halogen, and x is halogen such as fluorine, bromine, chlorine and the like.
In the method for preparing the electrolyte additive provided by the second aspect of the embodiment of the invention, the substituted terpyridine lithium ion complex is used as a reactant A, the substituted diphenyl phosphoacetylene lithium compound is used as a reactant B, and the reactant A and the reactant B are subjected to catalytic reaction under the action of the catalyst to obtain the electrolyte additive with the structural general formula I
Figure BDA0003164511610000114
Wherein R is1、R2、R3、R4、R5At least one selected from hydrogen, alkyl, alkenyl, alkynyl, alkoxy and halogen. The preparation method of the electrolyte additive provided by the embodiment of the invention is simple in process, is suitable for industrial large-scale production and application, and the prepared electrolyte additive has a flame retardant effect, is good in high-temperature thermal stability and not easy to generate gas, can form a compact, low-impedance and good-elasticity SEI film on the surface of an electrode, and improves the normal temperature/high temperature cycle performance, high temperature storage performance and safety performance of a battery, especially a high-nickel silicon carbon battery.
In some embodiments, the conditions of the catalytic reaction include: and (3) carrying out mixed reaction for 8-24 hours in a dark environment at the temperature of 60-90 ℃, so that the reactants A and B are fully reacted, the reaction is prevented from being influenced by illumination, and the generation of byproducts is reduced. If the reaction time is too short, the reaction of the reactant A and the reactant B is insufficient.
In some embodiments, the mole ratio of reactant a to reactant B is 1: (5-10). The molar ratio of the reactant A to the reactant B in the embodiment of the invention is favorable for full reaction between the reactant A and the reactant B, and if the addition ratio of the reactant A is too high or too low, byproducts are generated, and the yield of the additive is reduced.
In some embodiments, the catalyst is selected from at least one of cuprous iodide, cuprous bromide, cuprous chloride, palladium metal catalyst; these catalysts are all capable of catalyzing the reaction between reactant a and reactant B to form the electrolyte additive.
In some embodiments, in the reaction system after the reactant a, the reactant B, the catalyst and the first organic solvent are mixed and dissolved, the mass percentage concentration of the catalyst is 1-10%, and the amount of the catalyst can sufficiently ensure the reaction between the reactant a and the reactant B.
In some embodiments, the first organic solvent is selected from at least one of dichloromethane, diisopropylamine, diethylamine, dipropylamine, dibutylamine; the organic solvents have better dissolving effect on the reactant A and the reactant B, so that the reactants are fully dissolved in the organic solvents, full contact reaction between the reactants is facilitated, and an electrolyte additive product is obtained. In some embodiments, the first organic solvent is a mixed solvent of dichloromethane and diisopropylamine, diethylamine, dipropylamine or dibutylamine, and the dissolution of the reactants a and B and the reaction between the reactants can be better promoted by using two solvents with different polarities in a combined manner.
In some embodiments, the additives comprise:
Figure BDA0003164511610000131
Figure BDA0003164511610000132
Figure BDA0003164511610000133
at least one of (1). On one hand, the electrolyte additive provided by the embodiment of the invention can generate phosphorus-containing free radicals, has a flame-retardant effect, and improves the safety performance of the electrolyte. On the other hand, the electrolyte additive has high reduction potential and low oxidation potential, contains groups such as phosphorus-containing groups, alkyl, alkenyl, alkynyl, alkoxy, halogen and the like, is easy to generate electrochemical polymerization reaction on the surface of an electrode to form a compact SEI film with low impedance and good elasticity, can not crack in the process of lithium intercalation and deintercalation of materials, obviously improves the cycle performance of electrode materials, and improves the surfaces of positive and negative pole piecesThe stability of the interface prevents the solvent molecules from being reduced on the surface of the negative electrode and oxidized on the surface of the positive electrode. In addition, the additives have good high-temperature thermal stability, are not easy to generate gas under the high-temperature condition, and improve the normal-temperature/high-temperature cycle performance and high-temperature storage performance of the battery, particularly the high-nickel silicon carbon battery.
A third aspect of embodiments of the present invention provides an electrolyte including a lithium salt, a second organic solvent, and the additive described above.
The electrolyte provided by the third aspect of the embodiment of the invention comprises a lithium salt, an organic solvent and the electrolyte additive shown in the structural general formula I, and the additive not only has a flame retardant effect and good high-temperature cycle and storage stability, but also is not easy to generate gas, and an SEI film with good elasticity and low resistance is easily formed on the surface of an electrode, so that the cycle performance of an electrode material can be improved, the high-temperature cycle and storage performance of a battery can be improved, the safety performance of the battery can be improved, and the cycle life of the battery can be prolonged.
In some embodiments, the additive is present in the electrolyte in an amount of 0.1% to 10% by weight. The addition amount of the additive in the electrolyte in the embodiment of the invention enables the electrolyte to have the best flame retardant property, film-forming property and electrochemical comprehensive property. If the content of the additive is too high, the protective film layer formed on the surface of the electrode is too thick, the impedance is too high, the ion migration and transmission are not facilitated, and the electrochemical performance is reduced; if the content of the additive is too low, the flame retardant effect on the electrolyte is not obvious, the performance improvement on an SEI protective film layer formed on the surface of the electrode is not obvious, and the cycling stability of the electrode cannot be effectively improved.
In some embodiments, the additives comprise:
Figure BDA0003164511610000141
Figure BDA0003164511610000142
Figure BDA0003164511610000151
at least one of (1).
In some embodiments, the lithium salt is present in an amount of 10% to 15% by weight; the lithium salt of this content provides sufficient lithium ions for the electrolyte, ensuring the efficiency of the electrolyte.
In some embodiments, the lithium salt is selected from LiCF3SO3、LiC(CF3SO2)3、LiB(C2O4)2、LiF(C2O4)2、LiN(CF3SO2)2At least one of; the lithium salts are easy to dissociate into lithium ions, and the lithium ions are inserted into and taken out of the positive electrode and the negative electrode, so that the cyclic charge and discharge of the battery are realized.
In some embodiments, the electrolyte further comprises an auxiliary additive with a mass percentage of 0.1-5%, and if the auxiliary additive is added too much, the film forming resistance is too large, and the solubility is reduced; if the amount of the additive is too small, the auxiliary effect is not significant.
In some embodiments, the supplemental additive is selected from the group consisting of Vinylene Carbonate (VC), fluoroethylene carbonate (FEC), 1, 3-Propanesultone (PS), vinyl sulfate (DTD), 1-propene-1, 3-sultone (PES), Vinyl Ethylene Carbonate (VEC), tris (trimethylsilane) phosphite (TMSPi), tris (trimethylsilane) phosphate (TMSP), tris (trimethylsilane) borate (TMSB), lithium bis-fluorosulfonylimide (LiFSI), lithium difluorophosphate (LiPO)2F2) At least one of lithium difluorooxalate borate (LiODFB), lithium difluorooxalate phosphate (LiODFP), lithium bis (oxalato) borate (LiBOB), and Methylene Methanedisulfonate (MMDS); the high-temperature stability of the electrolyte is further improved through the auxiliary additives, the film forming effect of the electrolyte on the surface of an electrode is improved, and an electrolyte interphase (SEI) with excellent elasticity is formed on the surface of the electrode, so that the interface reaction on the surface of the electrode is prevented, and the stability and the safety performance of a battery are improved.
In some embodiments, the second organic solvent is selected from at least one of ethylene carbonate, methylethyl carbonate, diethyl carbonate, propylene carbonate, dimethyl carbonate, methyl formate, methyl acetate, methyl propionate, ethyl acetate, propyl propionate, sulfolane, γ -butyrolactone, dimethyl sulfoxide. The organic solvents have good compatibility with additives and lithium salts, and are beneficial to the transmission of lithium ions in the charging and discharging processes of the battery. In some embodiments, the organic solvent in the electrolyte may be formulated in various solvents, such as 25: 5: 60: 10 of a mixed organic solvent of Ethylene Carbonate (EC), Polycarbonate (PC), methylethyl carbonate (EMC) and diethyl carbonate (DEC), wherein EC is cyclic carbonate, having a high dielectric constant but a high viscosity, PC, EMC and DEC are linear esters, having a low viscosity but a low dielectric constant, and a balance between the viscosity of the solvent and the dielectric constant can be achieved by compounding, so that the ionic conductivity of the electrolyte is high and the viscosity is moderate.
In a fourth aspect of the embodiments of the present invention, a lithium ion battery is provided, where the lithium ion battery includes the above electrolyte.
The lithium ion battery provided by the fourth aspect of the embodiment of the invention can improve the flame retardant effect of the lithium ion battery, and can form an elastic SEI film on the surface of an electrode, thereby reducing the gas generation of the battery, improving the cycle performance of an electrode material, improving the interface stability of the surfaces of positive and negative pole pieces, and preventing the reduction of solvent molecules on the surface of a negative pole and the oxidation of the surface of a positive pole. Therefore, the high-temperature cycle and storage performance of the lithium ion battery are obviously improved, the safety performance of the battery is improved, and the cycle life of the battery is prolonged.
In the lithium ion battery of the embodiment of the invention, the anode, the cathode, the diaphragm and the like can be made of any materials meeting the requirements of practical application.
In some embodiments, the positive electrode material may be a high nickel ternary material, lithium cobaltate, or other ternary material, or may be a lithium cobalt oxide, a lithium nickel oxide, a lithium manganese oxide, a polyanion positive electrode material, or other ternary material. In some embodiments, the positive electrode material may be a high nickel material such as Ni83, Ni50, Ni60, Ni70, Ni80, Ni88, Ni 90.
In some embodiments, the anode material may be a silicon-based anode material, a graphite anode material, a tin-based anode material, or the like. In some embodiments, the negative electrode material may be carbon-coated silicon or silica, or a silicon-carbon negative electrode material in which carbon and silicon or silica are both mixed directly.
In some embodiments, the diaphragm may be a ceramic diaphragm, a rubberized diaphragm, or the like.
In order to clearly understand the details of the above-mentioned implementation and operation of the present invention by those skilled in the art and to obviously embody the advanced performance of the electrolyte additive, the preparation method thereof, the electrolyte and the lithium ion battery according to the embodiment of the present invention, the above-mentioned technical solution is exemplified by a plurality of embodiments.
Example 1
Electrolyte additiveThe preparation method comprises the following steps:
the reaction mixture of the reactant A1 is reacted,
Figure BDA0003164511610000171
(0.01mmol) and reactant B1,
Figure BDA0003164511610000172
(0.07mmol) was dissolved in distilled dichloromethane (80mL), diisopropylamine (1mL) was added, the mixture was degassed by bubbling nitrogen under sonication, and a catalytic amount of cuprous iodide (1mg) was added; the mixture was then stirred in the dark for 10 hours, water was added and the precipitate was separated off by filtration to give the additive PMN-1,
Figure BDA0003164511610000173
electrolyte solutionThe preparation method comprises the following steps: in a glove box with a water content of less than 1ppm and an oxygen content of less than 2ppm, 250g of ethylene carbonate EC, 50g of polycarbonate PC, 600g of ethyl methyl carbonate EMC, 100g of diethyl carbonate DEC were mixed and a suitable amount of well-dried LiPF was added6Enabling the concentration of lithium salt in the electrolyte to be 1mol/L to obtain a basic electrolyte; and adding 2% of PMN-1 into the basic electrolyte to obtain the electrolyte.
Lithium ion batteryThe manufacturing method comprises the following steps:
first, a positive electrode material Ni83, carbon black, a conductive agent CNT (carbon nanotube), and PVDF (polyvinylidene fluoride) were mixed in a ratio of 100: 0.7: 0.6: 1.5, coating the mixture on an aluminum foil with the thickness of 12 mu m, and drying the aluminum foil at the temperature of 85 ℃ to obtain a positive plate;
mixing a negative electrode graphite material, carbon black, SBR (styrene butadiene rubber) and CMC (carboxymethyl cellulose) according to a ratio of 100: 0.9: 1.9: 1, uniformly mixing and coating the mixture on a copper foil with the thickness of 8 mu m, and then drying the mixture at 90 ℃ to obtain a negative plate;
and thirdly, taking the ceramic diaphragm as a diaphragm, and manufacturing the positive and negative pole pieces into the battery in a winding or laminating mode. And (3) sealing the dry cell after injecting liquid, and standing at 45 ℃ for 48 hours to ensure that the electrolyte is fully soaked. The simulated cell was charged to 3.5V at 0.05C, then to 3.7V at 0.1C, then to 3.9V at 0.2C, and then aged at 45 ℃ for 48 h. And after aging, fully charging at 0.33C, and then discharging at 0.33C to 2.75V, namely obtaining the lithium ion battery.
Example 2
Electrolyte additiveThe preparation differs from example 1 in that: with the aid of the reactant a2, the reaction is,
Figure BDA0003164511610000181
and a reactant B2, and a reactant B,
Figure BDA0003164511610000182
as a reaction raw material, the additive PMN-2 is prepared.
Electrolyte solutionIt differs from example 1 in that: adding 2 percent of PMN-2 into the electrolyte,
Figure BDA0003164511610000183
lithium ion batteryThe difference from example 1 is that the electrolyte solution provided in example 2 was used.
Example 3
Electrolyte additiveThe preparation differs from example 1 in that: with the aid of the reactant a3, the reaction is,
Figure BDA0003164511610000184
and a reactant B3, and a reactant B,
Figure BDA0003164511610000185
as a reaction raw material, an additive PMN-3 is prepared,
Figure BDA0003164511610000191
electrolyte solutionIt differs from example 1 in that: 2 percent of PMN-3 is added into the electrolyte.
Lithium ion batteryThe difference from example 1 is that the electrolyte solution provided in example 3 was used.
Example 4
Electrolyte additiveThe preparation differs from example 1 in that: with the aid of the reactant a4, the reaction is,
Figure BDA0003164511610000192
and a reactant B4, and a reactant B,
Figure BDA0003164511610000193
as a reaction raw material, the additive PMN-4 is prepared.
Electrolyte solutionIt differs from example 1 in that: adding 2 percent of PMN-4 into the electrolyte,
Figure BDA0003164511610000194
lithium ion batteryThe difference from example 1 is that the electrolyte solution provided in example 4 was used.
Example 5
Electrolyte additiveThe preparation differs from example 1 in that: with the aid of the reactant a5, the reaction is,
Figure BDA0003164511610000195
and a reactant B5, and a reactant B,
Figure BDA0003164511610000196
as a reaction raw material, an additive PMN-5 is prepared,
Figure BDA0003164511610000201
electrolyte solutionIt differs from example 1 in that: 2 percent of PMN-5 is added into the electrolyte.
Lithium ion batteryThe difference from example 1 is that the electrolyte solution provided in example 5 was used.
Example 6
Electrolyte additiveThe preparation differs from example 1 in that: with the aid of the reactant a6, the reaction is,
Figure BDA0003164511610000202
and a reactant B6, and a reactant B,
Figure BDA0003164511610000203
as a reaction raw material, an additive PMN-6 is prepared,
Figure BDA0003164511610000204
electrolyte solutionIt differs from example 1 in that: 2 percent of PMN-6 is added into the electrolyte.
Lithium ion batteryThe difference from example 1 is that the electrolyte solution provided in example 6 was used.
Example 7
Electrolyte solutionIt differs from example 1 in that: 5% of PMN-1 is added into the electrolyte.
Lithium ion batteryThe difference from example 1 is that the electrolyte solution provided in example 7 was used.
Example 8
Electrolyte solutionIt differs from example 1 in that: 5% of PMN-2 is added into the electrolyte.
Lithium ion batteryThe difference from example 1 is that the electrolyte solution provided in example 8 was used.
Example 9
Electrolyte solutionIt differs from example 1 in that: 5 percent of PMN-3 and 0.5 percent of vinylene carbonate VC are added into the electrolyte.
Lithium ion batteryThe difference from example 1 is that the electrolyte solution provided in example 9 was used.
Example 10
Electrolyte solutionIt differs from example 1 in that: 5% of PMN-4 and 1% of fluoroethylene carbonate FEC were added to the electrolyte.
Lithium ion batteryThe difference from example 1 is that the electrolyte solution provided in example 10 was used.
Example 11
Electrolyte solutionIt differs from example 1 in that: 5% of PMN-5 and 2% of vinyl sulfate DTD are added into the electrolyte.
Lithium ion batteryThe difference from example 1 is that the electrolyte solution provided in example 11 was used.
Example 12
Electrolyte solutionIt differs from example 1 in that: the solvent in the electrolyte adopts a mixed solvent with the volume ratio of EC/EMC/DEC being 3/6/1, and the additive comprises 5 percent of PMN-6 and 1 percent of 1, 3-propane sultone PS.
Lithium ion batteryThe difference from example 1 is that the electrolyte solution provided in example 12 was used.
Example 13
Electrolyte solutionIt differs from example 1 in that: the solvent in the electrolyte adopts a mixed solvent with the volume ratio of EC/EMC/DEC being 3/6/1, and the additive comprises 5 percent of PMN-4 and 1 percent of lithium difluorophosphate LiPO2F2。
Lithium ion batteryThe difference from example 1 is that the electrolytic solution provided in example 13 was used.
Example 14
Electrolyte solutionDescription of the preferred embodimentsThe differences between 1 are: the solvent in the electrolyte adopts a mixed solvent with the volume ratio of EC/EMC/DEC being 3/6/1, and the additive comprises 5 percent of PMN-5 and 1 percent of lithium bis (fluorosulfonyl) imide LiFSI.
Lithium ion batteryThe difference from example 1 is that the electrolyte solution provided in example 14 was used.
Example 15
Electrolyte solutionIt differs from example 1 in that: the solvent in the electrolyte adopts a mixed solvent with the volume ratio of EC/EMC/DEC being 3/6/1, and the additive comprises 5 percent of PMN-6 and 0.2 percent of 1-propylene-1, 3-sultone PES.
Lithium ion batteryThe difference from example 1 is that the electrolyte solution provided in example 15 was used.
Example 16
Electrolyte solutionIt differs from example 1 in that: 10% of PMN-1 is added into the electrolyte.
Lithium ion batteryThe difference from example 1 is that the electrolyte solution provided in example 16 was used.
Example 17
Electrolyte solutionIt differs from example 1 in that: 0.1% of PMN-1 was added to the electrolyte.
Lithium ion batteryThe difference from example 1 is that the electrolytic solution provided in example 17 was used.
Example 18
Electrolyte solutionIt differs from example 1 in that: 11% of PMN-1 is added into the electrolyte.
Lithium ion batteryThe difference from example 1 is that the electrolyte solution provided in example 18 was used.
Comparative example 1
Electrolyte solutionIt differs from example 1 in that: no additives are added to the electrolyte.
Lithium ion batteryWhich is the same as that of example 1The difference lies in that: the electrolyte solution provided in comparative example 1 was used.
Comparative example 2
Electrolyte solutionIt differs from example 1 in that: to the electrolyte was added 2% fluoroethylene carbonate (FEC).
Lithium ion batteryIt differs from example 1 in that: the electrolyte used was the electrolyte provided in comparative example 2.
Further, in order to verify the advancement of the examples of the present invention, the following performance tests were performed on the lithium ion batteries prepared in examples 1 to 18 and comparative examples 1 to 2:
1. and (3) normal-temperature cycle test: the lithium ion batteries (5 for each condition, and the average value of the results) after aging and capacity grading are formed in each example and comparative example, and the lithium ion batteries are charged to 4.2V at 0.5C CC-CV in a constant temperature box at 25 +/-2 ℃, the current is cut off at constant voltage of 0.05C, the batteries are placed for 30min after charging, then discharged to 2.75V at 1C, and the batteries are placed for 30min, and the operation is continuously cycled for 300 times. The capacity retention (%) is a percentage obtained by dividing the discharge capacity after 600 cycles by the first discharge capacity.
2. High-temperature cycle test: the test temperature was 45. + -. 2 ℃ as the normal temperature cycle test.
3. And (3) high-temperature storage test: the lithium ion batteries after the aging and capacity grading of the compositions of the examples and comparative examples were completed (5 batteries for each condition, and the results were averaged) were charged to 4.2V with 0.5C CC-CV, the current was cut off from the constant voltage to 0.05C, and the charge capacity was recorded as C0. After the cells were stored at 55 ± 2 ℃ for 7 days and left to stand at room temperature for 5 hours, the cells were discharged to 2.75V at 1C, the discharge capacity was recorded as C1, and the capacity retention rate (%) was calculated as C1/C0 × 100%. Then, the cell was charged to 4.2V with 0.5C CC-CV, the current was cut off at 0.05C to fully charge the cell, the charge capacity was designated as C2, the cell was discharged to 2.75V with 1C, the discharge capacity was designated as C3, and the capacity recovery (%) was calculated as C3/C2 × 100%. The battery expansion (%) was calculated as a percentage obtained by subtracting the thickness before storage from the thickness after storage and dividing the obtained difference in thickness by the thickness before storage of the battery.
4. And (3) needle punching test: refer to the description of the test method for the needle-punched part in GB/T31485-2015.
The test results of the above performance test experiments are shown in table 1 below:
TABLE 1
Figure BDA0003164511610000241
Figure BDA0003164511610000251
According to the test results, the electrolyte of the lithium ion battery disclosed in the embodiment 1-18 is added with the PMN-1-PMN-6 terpyridyl diphenylphosphine acetylene metal ion complexing additive disclosed by the embodiment, so that the cycle stability and the storage performance of the lithium ion battery are obviously improved. At 25 ℃, the retention rate of the cycling capacity of the battery can reach 90%, and the cycling stability at normal temperature is good; at 45 ℃, the retention rate of the cycling capacity of the battery can reach 83%, and the battery has good high-temperature cycling stability. After the lithium ion batteries of all the embodiments are stored for seven days at a high temperature of 55 ℃, the batteries show higher retention rate which is as high as 94%; the recovery rate is high and reaches 97%, and the expansion rate is low and is not higher than 25%.
In addition, the electrolyte additive improves the probability of the lithium ion battery passing through the needling, and the probability of the battery passing through the needling is obviously improved along with the increase of the concentration of the additive in the electrolyte within the range of 0.1-10% of the mass percentage concentration of the additive in the electrolyte. However, as shown in example 18, when the content of the additive in the electrolyte is too high, the resistance to the battery increases too much, and the normal/high temperature cycle stability and storage stability of the battery are rather lowered.
When VC, FEC, DTD, PS and LiPO are added into the electrolyte at the same time2When auxiliary additives such as F2, LiFSI, PES and the like are used in a matched mode, the cooperation of the PMN-1-PMN-6 terpyridyl diphenylphosphine acetylene metal ion complex additive and the conventional auxiliary additive enables an SEI film to be more compact, and the electrochemical performance of the battery can be further improved.
And the electrolyte of the battery in the comparative example 1 is not added with the additive, and the electrolyte of the battery in the comparative example 2 is only added with the conventional fluoroethylene carbonate additive, so that the battery shows poorer conventional/high-temperature cycling stability and high-temperature storage stability, and has low passing rate and poor battery safety performance in a needling test.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. An electrolyte additive, comprising a compound having the general structural formula of formula I:
Figure FDA0003164511600000011
wherein R is1、R2、R3、R4、R5At least one selected from hydrogen, alkyl, alkenyl, alkynyl, alkoxy and halogen.
2. The electrolyte additive of claim 1 wherein the number of carbon atoms in the alkyl group, alkenyl group, alkynyl group, alkoxy group is not greater than 6;
and/or the halogen is selected from at least one of fluorine, chlorine and bromine.
3. The electrolyte additive of claim 1 or 2 wherein the additive comprises:
Figure FDA0003164511600000012
Figure FDA0003164511600000013
at least one of (1).
4. The preparation method of the electrolyte additive is characterized by comprising the following steps:
mixing and dissolving a reactant A, a reactant B, a catalyst and a first organic solvent, carrying out catalytic reaction, separating to obtain the additive with the structural general formula of the formula I,
Figure FDA0003164511600000021
wherein the structural formula of the reactant A is shown as
Figure FDA0003164511600000022
The structural formula of the reactant B is
Figure FDA0003164511600000023
Wherein R is1、R2、R3、R4、R5Is at least one of hydrogen, alkyl, alkenyl, alkynyl, alkoxy and halogen, and x is halogen.
5. The method of claim 4, wherein the catalytic reaction conditions comprise: mixing and reacting for 8-24 hours in a dark environment at the temperature of 60-90 ℃;
and/or the molar ratio of the reactant A to the reactant B is 1: (5-10);
and/or in a reaction system obtained by mixing and dissolving the reactant A, the reactant B, the catalyst and the first organic solvent, wherein the mass percentage concentration of the catalyst is 1-10%.
6. The method of preparing an electrolyte additive according to claim 4 or 5, wherein the catalyst is at least one selected from cuprous iodide, cuprous chloride, cuprous bromide, palladium metal catalyst;
and/or the first organic solvent is selected from at least one of dichloromethane, diisopropylamine, diethylamine, dipropylamine and dibutylamine;
and/or, the additive comprises:
Figure FDA0003164511600000031
Figure FDA0003164511600000032
Figure FDA0003164511600000033
at least one of (1).
7. An electrolyte comprising a lithium salt, a second organic solvent and an electrolyte additive as claimed in any one of claims 1 to 3 or prepared by a process as claimed in any one of claims 4 to 7.
8. The electrolyte of claim 7, wherein the additive is present in the electrolyte in an amount of 0.1% to 10% by weight;
and/or the mass percentage content of the lithium salt is 10-15%;
and/or the electrolyte also comprises 0.1-5% of auxiliary additive by mass percent.
9. The electrolyte of claim 8, wherein the lithium salt is selected from the group consisting of LiCF3SO3、LiC(CF3SO2)3、LiB(C2O4)2、LiF(C2O4)2、LiN(CF3SO2)2At least one of;
and/or the auxiliary additive is selected from at least one of vinylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone, vinyl sulfate, 1-propylene-1, 3-sultone, ethylene carbonate, tris (trimethylsilane) phosphite, lithium bis-fluorosulfonylimide, lithium difluorophosphate and lithium difluorooxalato borate;
and/or the second organic solvent is at least one selected from ethylene carbonate, methyl ethyl carbonate, diethyl carbonate, propylene carbonate, dimethyl carbonate, methyl formate, methyl acetate, methyl propionate, ethyl acetate, propyl propionate, sulfolane, gamma-butyrolactone and dimethyl sulfoxide.
10. A lithium ion battery comprising the electrolyte according to any one of claims 7 to 9.
CN202110800463.6A 2021-07-15 2021-07-15 Electrolyte additive, preparation method thereof, electrolyte and lithium ion battery Active CN113506915B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110800463.6A CN113506915B (en) 2021-07-15 2021-07-15 Electrolyte additive, preparation method thereof, electrolyte and lithium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110800463.6A CN113506915B (en) 2021-07-15 2021-07-15 Electrolyte additive, preparation method thereof, electrolyte and lithium ion battery

Publications (2)

Publication Number Publication Date
CN113506915A true CN113506915A (en) 2021-10-15
CN113506915B CN113506915B (en) 2022-10-18

Family

ID=78013447

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110800463.6A Active CN113506915B (en) 2021-07-15 2021-07-15 Electrolyte additive, preparation method thereof, electrolyte and lithium ion battery

Country Status (1)

Country Link
CN (1) CN113506915B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115073497A (en) * 2021-03-16 2022-09-20 恒大新能源技术(深圳)有限公司 Polynitrogen heterocyclic compound, preparation method thereof, electrolyte and secondary battery

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002008716A (en) * 2000-06-22 2002-01-11 Mitsubishi Chemicals Corp Nonaqueous electrolyte and nonaqueous electrolyte secondary battery
US20020025477A1 (en) * 2000-07-14 2002-02-28 Mitsubishi Chemical Corporation Non-aqueous electrolytic solution and secondary battery containing same
CN111205322A (en) * 2020-01-11 2020-05-29 山东理工大学 2,4, 6-trioxo-1, 3, 5-triazine-lithium triphosphate and compound thereof used for preparing flame-retardant electrolyte
CN112838270A (en) * 2021-03-18 2021-05-25 合肥国轩高科动力能源有限公司 Electrolyte additive for improving high-temperature flatulence of battery, electrolyte and lithium ion battery containing electrolyte
CN112928331A (en) * 2021-02-20 2021-06-08 集美大学 Electrolyte for lithium-sulfur battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002008716A (en) * 2000-06-22 2002-01-11 Mitsubishi Chemicals Corp Nonaqueous electrolyte and nonaqueous electrolyte secondary battery
US20020025477A1 (en) * 2000-07-14 2002-02-28 Mitsubishi Chemical Corporation Non-aqueous electrolytic solution and secondary battery containing same
CN111205322A (en) * 2020-01-11 2020-05-29 山东理工大学 2,4, 6-trioxo-1, 3, 5-triazine-lithium triphosphate and compound thereof used for preparing flame-retardant electrolyte
CN112928331A (en) * 2021-02-20 2021-06-08 集美大学 Electrolyte for lithium-sulfur battery
CN112838270A (en) * 2021-03-18 2021-05-25 合肥国轩高科动力能源有限公司 Electrolyte additive for improving high-temperature flatulence of battery, electrolyte and lithium ion battery containing electrolyte

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115073497A (en) * 2021-03-16 2022-09-20 恒大新能源技术(深圳)有限公司 Polynitrogen heterocyclic compound, preparation method thereof, electrolyte and secondary battery

Also Published As

Publication number Publication date
CN113506915B (en) 2022-10-18

Similar Documents

Publication Publication Date Title
CN113013492B (en) Organic electrolyte with wide working temperature area and sodium ion battery
CN114583270A (en) Lithium ion battery
CN113851713B (en) Electrolyte additive, electrolyte containing additive and lithium ion battery
CN115799643B (en) Nonaqueous electrolyte, lithium ion battery, battery module, battery pack, and power utilization device
CN111116651B (en) Phosphite ester compound containing thienyl and application thereof
CN110416611B (en) Non-aqueous electrolyte of lithium ion battery and lithium ion battery using same
CN110190330B (en) Lithium battery, electrolyte thereof and preparation method of electrolyte
CN113506916B (en) Electrolyte additive, electrolyte and secondary battery
CN114976240A (en) Borate lithium salt electrolyte and lithium ion battery
CN113506915B (en) Electrolyte additive, preparation method thereof, electrolyte and lithium ion battery
CN112701353A (en) Electrolyte and application thereof
CN111106341B (en) Lithium ion battery containing high-nickel cathode material
CN116525952A (en) Nonaqueous electrolyte and sodium ion battery
CN107732302A (en) A kind of nonaqueous electrolytic solution and its preparation method and application
CN111864253B (en) Lithium ion battery electrolyte and lithium ion battery
CN110247116B (en) Non-aqueous electrolyte of lithium ion battery and lithium ion battery using same
CN113328144A (en) Lithium ion battery electrolyte and lithium ion battery using same
CN113801074A (en) Electrolyte additive, preparation method thereof, electrolyte and secondary battery
CN114335729B (en) High-voltage additive for lithium battery and electrolyte
CN115224360A (en) Electrolyte additive, preparation method thereof, electrolyte and lithium ion battery
CN110911747B (en) Electrolyte additive, electrolyte and lithium ion battery
WO2024012244A1 (en) Local high-concentration electrolyte, secondary battery, electronic device, and mobile apparatus
CN117374387A (en) Electrolyte for secondary battery, electrolyte additive, and secondary battery
CN117239238A (en) Electrolyte and lithium ion battery thereof
CN113972394A (en) Electrolyte and lithium ion battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant