CN114695957A - Preparation method and application of novel electrolyte additive containing fluorine, boron and phosphorus - Google Patents

Preparation method and application of novel electrolyte additive containing fluorine, boron and phosphorus Download PDF

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CN114695957A
CN114695957A CN202011614315.7A CN202011614315A CN114695957A CN 114695957 A CN114695957 A CN 114695957A CN 202011614315 A CN202011614315 A CN 202011614315A CN 114695957 A CN114695957 A CN 114695957A
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carbonate
compound
lithium
electrolyte
electrolyte additive
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张忠如
马国强
严红
徐冲
沈方烈
廖颖
杨勇
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Zhejiang Chemical Industry Research Institute Co Ltd
Xiamen University
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Zhejiang Chemical Industry Research Institute Co Ltd
Xiamen University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte

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Abstract

The invention discloses a novel electrolyte additive containing fluorine, boron and phosphorus, a preparation method and application thereof, wherein the structure of the novel electrolyte additive is selected from at least one of the following formulas (I), (II) and (III):

Description

Preparation method and application of novel electrolyte additive containing fluorine, boron and phosphorus
Technical Field
The invention relates to the field of batteries, in particular to a lithium ion battery, and particularly relates to a novel electrolyte additive containing fluorine, boron and phosphorus, a preparation method of the novel electrolyte additive and application of the novel electrolyte additive as an electrolyte additive.
Background
Lithium ion batteries, which have been the highest specific energy secondary batteries up to now, are widely used as power sources or power batteries for portable electronic devices, such as: mobile phones, notebook computers, digital cameras and even new energy vehicles. The lithium ion battery mainly comprises a positive electrode, a negative electrode, electrolyte, a diaphragm and other accessories, and has the advantages of high specific energy density, high working voltage, long cycle life, low self-discharge rate, no memory effect and the like.
Service life and safety problems are core technologies and problems of power secondary batteries, but high-temperature performance is a technical problem which needs to be particularly concerned in consideration of differences of regional environments and heat release conditions of batteries, whether lithium ion batteries, sodium ion batteries or other types of batteries.
The sulfuric acid ester substance, such as the vinyl sulfate (DTD), has a good effect of improving the high-temperature performance of the battery, and can inhibit the battery from flatulence. However, when the sulfate is used as an electrolyte additive, internal resistance is easily increased, and other side reactions may be caused, so that polarization is increased in the battery circulation process.
Therefore, there is a need for an electrolyte additive that can improve both the high temperature performance and the cycle performance of a battery.
Disclosure of Invention
In order to solve the technical problems, the invention provides a novel electrolyte additive containing fluorine, boron and phosphorus, which can improve the high-temperature performance and the cycle performance of a battery at the same time.
The inventor researches and discovers that the fluorine-containing phosphate compound has better low-temperature and rate-multiplying performance, such as lithium difluorophosphate, lithium monofluorophosphate and the like, but the solubility of the compound in an organic solvent is very low due to the structural problem of the compound, generally speaking, the solubility is not higher than 1 wt% in a conventional carbonate solvent, so that the application of the compound in an electrolyte is greatly limited. The boron-containing lithium salt represented by lithium bis (oxalato) borate and lithium difluoro (oxalato) borate can improve the cycling stability, high voltage and high temperature performance of the battery. The invention combines a plurality of elements containing fluorine, boron and phosphorus into one compound simultaneously, improves the solubility of the compound in organic solvents (such as carbonic ester), and can realize the solubility of 5 wt% at most in the conventional carbonic ester solvent; and simultaneously, the advantages of functional groups containing fluorine, boron and phosphorus are utilized, so that the high-temperature performance and the cycle performance of the battery are simultaneously improved.
The purpose of the invention is realized by the following technical scheme:
a novel electrolyte additive containing fluorine, boron and phosphorus, the novel electrolyte additive having a structure selected from at least one of the following formulae (I), (II) and (III):
Figure BDA0002874359440000021
wherein M is independently selected from Li, Na, K, Rb, Cs, Ca, Mg; n is 1 or 2. Preferably, M is independently selected from Li, Na or K, and n is 1.
Specifically, the novel electrolyte additive is selected from at least one of the following 7 structures:
Figure BDA0002874359440000022
Figure BDA0002874359440000031
the invention also provides a preparation method of the novel electrolyte additive, which comprises the following steps:
A1. adding a boron-containing compound and fluorophosphate into a first solvent, stirring for reaction, and filtering to obtain a crude additive product.
Further, the obtained crude additive is purified, and therefore, the preparation method further comprises:
A2. adding the crude additive into a second solvent, dissolving and filtering to obtain filtrate;
A3. and concentrating the filtrate, adding a third solvent to precipitate a solid, and filtering again to obtain the solid serving as the novel electrolyte additive.
The boron-containing compound is a boron trifluoride complex and/or boron trifluoride gas.
The fluorophosphate is selected from at least one of lithium monofluorophosphate, sodium monofluorophosphate, potassium monofluorophosphate, calcium monofluorophosphate and magnesium monofluorophosphate, and is preferably lithium monofluorophosphate and sodium monofluorophosphate.
The molar ratio of the boron-containing compound to the fluorophosphate is 0.5-4.5: 1, the reaction temperature is 0-120 ℃.
The first solvent is at least one selected from dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and ethyl acetate, and is preferably dimethyl carbonate.
The second solvent is at least one selected from acetonitrile, acetone, dimethyl sulfoxide and N-methyl pyrrolidone, and is preferably acetonitrile.
The third solvent is at least one selected from dichloromethane, toluene, xylene and petroleum ether, and is preferably dichloromethane.
The invention can realize the preparation of different products by adjusting the raw material ratio and the reaction temperature.
In one embodiment, the reaction temperature is controlled to be 0 to 40 ℃, and the molar ratio of the boron-containing compound to the fluorophosphate is 0.5 to 1.1: 1, the reaction product is mainly a cyclic product compound 3, 5 or 7, such as compound 3, the reaction formula is as follows:
Figure BDA0002874359440000041
in another specific embodiment, the temperature is controlled to be 80-120 ℃, and the molar ratio of the boron-containing compound to the fluorophosphate is 0.5-1.1: 1, the reaction tends to produce a more thermodynamically stable product compound 2, 4 or 6, such as compound 2, the reaction formula of which is as follows:
Figure BDA0002874359440000042
in another embodiment, the temperature is controlled to be 80-120 ℃, and the molar ratio of the boron-containing compound to the fluorophosphate is 1.9-2.1: 1, the reaction is more prone to produce ester product compound 1, the reaction formula is as follows:
Figure BDA0002874359440000043
when the reaction temperature and the charge ratio are outside the above ranges, the reaction products are a mixture, which brings about a certain difficulty in product separation. In addition, the addition of more boron-containing compound will react with the lithium fluoride produced to produce lithium tetrafluoroborate, further increasing the difficulty of product separation. In these cases, the resulting mixture can be used as a novel electrolyte additive, but is not preferred.
The invention also provides a lithium ion battery electrolyte, which comprises the novel electrolyte additive, and the dosage of the novel electrolyte additive accounts for 0.05-8.0% of the total amount of the electrolyte. Preferably, the dosage of the novel electrolyte additive accounts for 0.1-2.0% of the total amount of the electrolyte.
The lithium ion battery electrolyte further comprises:
and the lithium salt is the lithium salt commonly used in the electrolyte. Preferably, the lithium salt is at least one selected from lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide and lithium bis (trifluoromethylsulfonyl) imide, and the molar concentration of the lithium salt is 0.4-3 mol/L, preferably 0.8-1.6 mol/L;
the organic solvent is at least one selected from a carbonate or fluoro carbonate compound of C3-C6, a carboxylic ester or fluoro carboxylic ester compound of C3-C8, a sulfone compound, an ether compound and a nitrile compound.
The carbonate or fluoro carbonate compound of C3-C6 is at least one selected from ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, fluoro ethylene carbonate and difluoro ethylene carbonate;
the carboxylic ester or fluorinated carboxylic ester compound of C3-C8 is at least one selected from gamma-butyrolactone, methyl acetate, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, ethyl butyrate, propyl acetate, propyl propionate and fluorinated ethyl acetate;
the sulfone compound is at least one selected from sulfolane, dimethyl sulfoxide, dimethyl sulfone and diethyl sulfone;
the ether compound is at least one selected from ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, 1, 3-dioxolane, 1, 4-dioxahexane, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and 1, 1,2, 2-tetrafluoroethyl-2, 2, 3, 3-tetrafluoropropyl ether.
The nitrile compound is selected from at least one of succinonitrile, adiponitrile, phenylacetonitrile, 1, 2-dicyanoethoxyethane and 1,3, 6-hexanetricarbonitrile.
In order to further improve the performance of the battery, the lithium ion battery electrolyte further comprises a basic additive, wherein the basic additive is at least one selected from carbonate compounds, fluoro carbonate compounds, sulfate compounds, sulfonate compounds, borate compounds, phosphate compounds and fluorine-containing lithium salt compounds.
The carbonate compound is selected from Vinylene Carbonate (VC) and/or Vinyl Ethylene Carbonate (VEC);
the fluoro carbonate compound is at least one selected from Fluoro Ethylene Carbonate (FEC), trifluoro propylene carbonate (TFPC), Fluoro Ethyl Methyl Carbonate (FEMC), fluoro diethyl carbonate (FDEC) and fluoro dimethyl carbonate (FDMC);
the sulfate compound is at least one selected from vinyl sulfate (DTD), 4-methyl vinyl sulfate and 4-ethyl vinyl sulfate;
the sulfonate compound is selected from at least one of 1, 3-Propane Sultone (PS), 1, 3-Propene Sultone (PST), 1, 4-Butane Sultone (BS) and Methylene Methane Disulfonate (MMDS);
the borate compound is selected from at least one of tri (trimethylsilyl) borate (TMSB), triethyl borate, tripropyl borate, tributyl borate and triallyl borate;
the phosphate compound is at least one selected from tris (trimethylsilyl) phosphate (TMSP), triallyl phosphate, tripropargyl phosphate and tris (trimethylsilyl) phosphite;
the fluorine-containing lithium salt compound is selected from lithium difluorophosphate (LiPF)2O2) Lithium tetrafluoroborate (LiBF)4) Lithium bis (fluorosulfonyl) imide (LiFSI), lithium tetrafluoro oxalate phosphate, lithium difluoro bis (oxalate) phosphate (LiDFOP), lithium difluoro oxalate borate (LiDFOB), lithium tris (oxalate) phosphate, and the fluorine-containing lithium salt compound is different from the lithium salt.
The invention also provides a lithium ion battery which comprises a positive electrode, a negative electrode, a diaphragm and any one of the lithium ion battery electrolytes.
The positive active material is a nickel-cobalt-manganese ternary material or a nickel-cobalt-aluminum ternary material or a lithium cobaltate material or a lithium iron phosphate material; wherein the nickel-cobalt-manganese ternary material is Li (Ni)xCoyMnz)O 2，x≥0.5，y>0，z>0, x + y + z ═ 1; the nickel-cobalt-aluminum ternary material is Li (Ni)xCoyAlz)O 2，x≥0.8，y>0，z>0，x+y+z＝1。
The negative active material is graphite, silicon carbon, silicon monoxide, silicon, tin, metal lithium or a composite material thereof.
Compared with the prior art, the invention has the beneficial effects that:
the novel electrolyte additive containing fluorine, boron and phosphorus combines fluorine, boron and phosphorus in the same compound, so that a single compound has the performances of the three functional groups, and the high-temperature performance and the cycle performance of a battery can be improved simultaneously.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Preparation example 1
The present preparation example provides the preparation of a novel electrolyte additive (compound 5) containing fluorine, boron and phosphorus, in which the molar ratio of the raw material boron triborate gas to sodium monofluorophosphate was 1: 1.
143.9g (1mol) of anhydrous sodium monofluorophosphate (with the purity of 99%) and 300g of a first dimethyl carbonate solvent are added into a reaction bottle with a thermometer, and stirring is started to uniformly mix the system; and introducing 68g (1mol) of boron trifluoride gas into the reaction bottle, heating to 40 ℃ after the introduction is finished, keeping the temperature for reaction for 24 hours, filtering the reaction liquid to obtain a white solid, and drying to obtain 161g of an additive crude product.
Dissolving the crude additive by 300g of anhydrous acetonitrile, stirring for 0.5h, discarding the solid, transferring the filtrate into a flask, slowly adding 400g of dichloromethane into the flask under stirring, and gradually precipitating white solid from the solution. After the dichloromethane is added, stirring for 0.5h at room temperature, filtering and drying to obtain a solid, namely the novel electrolyte additive containing fluorine, boron and phosphorus, which is marked as FBP-1.
Preparation example 2
The procedure of this preparation is the same as that of preparation 1 except that: a novel electrolyte additive (Compound 3), noted FBP-2, was prepared using 111.8g (1mol) of anhydrous lithium monofluorophosphate in place of the anhydrous sodium monofluorophosphate used in preparation example 1.
Preparation example 3
The procedure of this preparation is the same as that of preparation 1 except that: a novel electrolyte additive (Compound 7), noted FBP-3, was prepared using 192.1g (1mol) of anhydrous potassium monofluorophosphate in place of the anhydrous sodium monofluorophosphate in preparation example 1.
Preparation example 4
The procedure of this preparation is the same as that of preparation 2 except that: the reaction temperature was adjusted to 100 ℃ to prepare a novel electrolyte additive (compound 2) noted FBP-4.
Preparation example 5
The procedure of this preparation is the same as that of preparation 4 except that: adjusting the molar ratio of boron trifluoride gas to lithium monofluorophosphate to be 2: 1, specifically: boron trifluoride gas (136 g, 2mol) and lithium monofluorophosphate (111.8 g, 1mol) were prepared to obtain a novel electrolyte additive (Compound 1) which is denoted as FBP-5.
Firstly, preparation of electrolyte
Preparing a basic electrolyte: in an argon-filled glove box (moisture < 5ppm, oxygen < 10ppm), Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC) were mixed in the mass ratio EC: EMC: DEC ═ 3:5:2 was mixed homogeneously and lithium hexafluorophosphate (LiPF) was added slowly to the mixed solution6) To LiPF6The molar concentration of (a) was 1.1mol/L, and a base electrolyte was obtained.
Example 1: to the base electrolyte, 0.5% of FBP-2 was added to obtain an electrolyte of this example.
Example 2: to the base electrolyte, FBP-2 was added in an amount of 1.0% to obtain an electrolyte of the present example.
Example 3: to the base electrolyte, 0.5% of FBP-4 was added to obtain an electrolyte of this example.
Example 4: to the base electrolyte, FBP-4 was added in an amount of 1.0% to obtain an electrolyte of the present example.
Example 5: to the base electrolyte, FBP-5 was added in an amount of 1.0% to obtain an electrolyte of the present example.
Example 6: to the base electrolyte, 1.0% of FBP-2 and 1.0% of Vinylene Carbonate (VC) were added to obtain an electrolyte of this example.
Example 7: to the base electrolyte, 1.0% of FBP-2 and 2.0% of fluoroethylene carbonate (FEC) were added to obtain an electrolyte of the present example;
example 8: to the base electrolyte, 1.0% of FBP-2 and 1.0% of vinyl sulfate (DTD) were added to obtain an electrolyte of the present example;
example 9: to the base electrolyte, 1.0% of FBP-2 and 1.0% of 1, 3-Propanesultone (PS) were added to obtain an electrolyte of the present example;
example 10: to the base electrolyte, 1.0% of FBP-2 and 1.0% of lithium difluorophosphate (LiPF) were added2O2) Obtaining the electrolyte of the embodiment;
example 11: to the base electrolyte, 1.0% of FBP-2 and 1.0% of tris (trimethylsilane) borate (TMSB) were added to obtain an electrolyte of this example;
example 12: to the base electrolyte, 1.0% of FBP-2 and 1.0% of tris (trimethylsilane) phosphate (TMSP) were added to obtain an electrolyte of this example;
example 13: to the base electrolyte, 1.0% of FBP-4 and 1.0% of Vinylene Carbonate (VC) were added to obtain an electrolyte of this example.
Example 14: to the base electrolyte, 1.0% of FBP-4 and 1.0% of vinyl sulfate (DTD) were added to obtain an electrolyte of this example.
Comparative example 1: this comparative example is identical to the base electrolyte.
Comparative example 2: to the base electrolyte, 1.0% of VC was added to obtain an electrolyte of this comparative example.
Comparative example 3: to the base electrolyte, 2.0% of FEC was added to obtain an electrolyte of this comparative example.
Comparative example 4: to the base electrolyte, 1.0% of DTD was added to obtain an electrolyte of this comparative example.
Comparative example 5: to the base electrolyte, 1.0% of PS was added to obtain an electrolyte of this comparative example.
Comparative example 6: 1.0% of LiPF is added to the base electrolyte2O2The electrolyte of this comparative example was obtained.
Comparative example 7: to the base electrolyte, 1.0% of TMSB was added to obtain an electrolyte of this comparative example.
Comparative example 8: to the base electrolyte, 1.0% of TMSP was added to obtain an electrolyte of this comparative example.
Second, performance test
The lithium ion battery electrolytes of the above examples and comparative examples were separately preparedThe lithium ion power battery with the soft package capacity of 1000mAh is manufactured, the lithium ion power battery comprises a positive pole piece, a negative pole piece, a diaphragm, electrolyte and battery auxiliary materials, and the positive active material is a nickel-cobalt-manganese ternary material or a nickel-cobalt-aluminum ternary material or a lithium cobaltate material or a lithium iron phosphate material; wherein the positive active material is high-nickel ternary positive LiNi0.83Co0.07Mn0.2O2The negative active material is high capacity graphite. The preparation process comprises the following steps: winding the positive pole piece, the diaphragm and the negative pole piece together into a roll core, sealing by using an aluminum plastic film, baking to enable the electrode moisture to meet the requirement, injecting electrolyte into the baked battery cell, and performing standing, formation, capacity grading and aging processes to obtain the finished soft package battery cell.
The prepared lithium ion power battery (soft package battery core) is subjected to performance test, and the test results are shown in the following table 1:
TABLE 1 Battery Performance test results
Figure BDA0002874359440000111
The data clearly show that the novel electrolyte additive containing fluorine, boron and phosphorus can obviously improve the high-temperature storage performance and the high-temperature cycle performance of the battery, and mainly shows that the capacity recovery rate of the battery after high-temperature storage is improved, the volume expansion of the battery in high-temperature storage is inhibited, the capacity retention rate of the battery in high-temperature cycle is improved, and the DCR increase of the battery in the cycle process is inhibited. In addition, the data show that increasing the additive amount further improves the high-temperature storage performance of the battery but shows a small amount of degradation in the high-temperature cycle performance.
The novel electrolyte additive containing fluorine, boron and phosphorus is combined with basic additive, such as VC, FEC, DTD, PS, LiPO2F2TMSP, TMSB, etc., the high temperature storage and high temperature cycling performance of the cell is significantly better than that of cells containing only the base additive.

Claims (16)

1. A novel electrolyte additive containing fluorine, boron and phosphorus is characterized in that: the structure of the novel electrolyte additive is selected from at least one of the following formulas (I), (II) and (III):
Figure FDA0002874359430000011
wherein M is independently selected from Li, Na, K, Rb, Cs, Ca, Mg; n is 1 or 2.
2. The novel electrolyte additive containing fluorine, boron and phosphorus according to claim 1, characterized in that: m is independently selected from Li, Na or K, and n is 1.
3. The method for preparing a novel electrolyte additive according to claim 1 or 2, characterized in that: the preparation method comprises the following steps:
A1. adding the boron-containing compound and fluorophosphate into a first solvent, heating for reaction, and filtering to obtain a crude additive product.
4. The method for preparing a novel electrolyte additive according to claim 3, wherein: the preparation method further comprises the following steps:
A2. adding the crude additive into a second solvent, heating for dissolving, and filtering to obtain a filtrate;
A3. and adding a third solvent into the filtrate to precipitate a solid, and filtering again to obtain the solid which is the novel electrolyte additive.
5. The method for preparing a novel electrolyte additive according to claim 3 or 4, wherein: the boron-containing compound is selected from a boron trifluoride complex and/or a boron trifluoride gas.
6. The method for preparing a novel electrolyte additive according to claim 3 or 4, characterized in that: the fluorophosphate is selected from at least one of lithium monofluorophosphate, sodium monofluorophosphate, potassium monofluorophosphate, calcium monofluorophosphate and magnesium monofluorophosphate.
7. The method for preparing a novel electrolyte additive according to claim 3 or 4, characterized in that: the molar ratio of the boron-containing compound to the fluorophosphate is 0.5-4.5: 1.
8. the method for preparing a novel electrolyte additive according to claim 3 or 4, characterized in that: the first solvent is at least one selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethyl acetate, ethyl propionate, methyl propionate and methyl acetate.
9. The method for preparing a novel electrolyte additive according to claim 4, wherein: the second solvent is at least one selected from acetonitrile, acetone, dimethyl sulfoxide and N-methyl pyrrolidone; the third solvent is at least one selected from dichloromethane, toluene, xylene and petroleum ether.
10. The method for preparing a novel electrolyte additive according to claim 3 or 4, characterized in that: the reaction temperature of the step A1 is 0-120 ℃.
11. A lithium ion battery electrolyte is characterized in that: the lithium ion battery electrolyte comprises the novel electrolyte additive disclosed in claim 1 or 2, and the novel electrolyte additive is used in an amount of 0.05-8.0% of the total amount of the electrolyte.
12. The lithium ion battery electrolyte of claim 11, wherein: the lithium ion battery electrolyte further comprises:
the lithium salt is selected from at least one of lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide and lithium bis (trifluoromethylsulfonyl) imide, and the molar concentration of the lithium salt is 0.4-3 mol/L;
the organic solvent is at least one selected from a carbonate or fluoro carbonate compound of C3-C6, a carboxylic ester or fluoro carboxylic ester compound of C3-C8, a sulfone compound, an ether compound and a nitrile compound.
13. The lithium ion battery electrolyte of claim 12, wherein:
the carbonate or fluoro carbonate compound of C3-C6 is at least one selected from ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, fluoro ethylene carbonate and difluoro ethylene carbonate;
the carboxylic ester or fluorinated carboxylic ester compound of C3-C8 is at least one selected from gamma-butyrolactone, methyl acetate, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, ethyl butyrate, propyl acetate, propyl propionate and fluorinated ethyl acetate;
the sulfone compound is at least one selected from sulfolane, dimethyl sulfoxide, dimethyl sulfone and diethyl sulfone;
the ether compound is at least one selected from ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, 1, 3-dioxolane, 1, 4-dioxahexane, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and 1, 1,2, 2-tetrafluoroethyl-2, 2, 3, 3-tetrafluoropropyl ether.
The nitrile compound is selected from at least one of succinonitrile, adiponitrile, phenylacetonitrile, 1, 2-dicyanoethoxyethane and 1,3, 6-hexanetricarbonitrile.
14. The lithium ion battery electrolyte of claim 12, wherein: the lithium ion battery electrolyte further comprises a basic additive, wherein the basic additive is selected from at least one of carbonate compounds, fluoro carbonate compounds, sulfate compounds, sulfonate compounds, borate compounds, phosphate compounds and fluorine-containing lithium salt compounds.
15. The lithium ion battery electrolyte of claim 14, wherein:
the carbonate compound is selected from vinylene carbonate and/or ethylene carbonate;
the fluoro carbonate compound is at least one of fluoro ethylene carbonate, trifluoro propylene carbonate, fluoro ethyl methyl carbonate, fluoro diethyl carbonate and fluoro dimethyl carbonate;
the sulfate compound is at least one selected from vinyl sulfate, 4-methyl vinyl sulfate and 4-ethyl vinyl sulfate;
the sulfonate compound is at least one selected from 1, 3-propane sultone, 1, 3-propylene sultone, 1, 4-butane sultone and methylene methanedisulfonate;
the borate compound is selected from at least one of tri (trimethylsilyl) borate, triethyl borate, tripropyl borate, tributyl borate and triallyl borate;
the phosphate compound is at least one selected from tri (trimethylsilyl) phosphate, triallyl phosphate, tripropargyl phosphate and tri (trimethylsilyl) phosphite;
the fluorine-containing lithium salt compound is at least one selected from lithium difluorophosphate, lithium tetrafluoroborate, lithium difluorosulfimide, lithium tetrafluoro oxalate phosphate, lithium difluorobis oxalate phosphate, lithium difluorooxalate borate and lithium tris oxalate phosphate, and is different from the lithium salt.
16. A lithium ion battery comprises a positive electrode, a negative electrode and a diaphragm, and is characterized in that: the battery further comprises the lithium ion battery electrolyte of any of claims 11-15.
CN202011614315.7A 2020-12-31 2020-12-31 Preparation method and application of novel electrolyte additive containing fluorine, boron and phosphorus Pending CN114695957A (en)

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