CN110858665A - Lithium ion battery electrolyte and application thereof - Google Patents

Lithium ion battery electrolyte and application thereof Download PDF

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CN110858665A
CN110858665A CN201810971191.4A CN201810971191A CN110858665A CN 110858665 A CN110858665 A CN 110858665A CN 201810971191 A CN201810971191 A CN 201810971191A CN 110858665 A CN110858665 A CN 110858665A
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lithium
ion battery
electrolyte
lithium ion
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陈黎
甘朝伦
秦虎
王婷婷
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Zhangjiagang Guotai Huarong New Chemical Materials Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—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
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    • H01M2300/0025—Organic electrolyte
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Abstract

The invention relates to a lithium ion battery electrolyte, which comprises a solvent, lithium salt and an additive, wherein the additive comprises lithium difluorobis (malonate) phosphate and derivatives thereof shown in a structural formula (1) and/or lithium tetrafluoromalonate phosphate and derivatives thereof shown in a structural formula (2);
Figure DDA0001776239360000011
(2) (ii) a Wherein Rx, Ry and Rz each independently represents an oxygen atom,
Figure DDA0001776239360000012
Or

Description

Lithium ion battery electrolyte and application thereof
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a lithium ion battery electrolyte and application thereof.
Background
In recent years, lithium ion batteries have gradually replaced traditional batteries such as lead-acid batteries, nickel-cadmium batteries, nickel-hydrogen batteries and the like due to the characteristics of high energy density, long cycle life, environmental friendliness and the like. However, as portable electronic products are miniaturized and multifunctional, the energy density of lithium ion batteries is required to be higher and higher, and increasing the operating voltage of lithium ion batteries is one of the most effective methods for increasing the energy density. The carbonate solvents commonly used at present have a narrow electrochemical window, are easily decomposed at high voltage, and the reaction between the positive electrode and the electrolyte is also promoted, which finally causes the deterioration of the battery.
In view of the above, there is a need for a safe electrolyte with good high voltage performance.
At present, there are many reports on methods for improving the charge and discharge performance of a 5V lithium ion battery, for example, Zhang et al report a series of fluorinated organic carbonate solvents, and it is found that after fluorine element is introduced into the carbonate solvent for substitution, the oxidation resistance of the fluorine-containing carbonate can be obviously improved. Fluoroethylene carbonate, methyl-2, 2, 2-trifluoroethyl carbonate and ethyl-2, 2, 2-trifluoroethyl carbonate have oxidation potentials much higher than that of non-fluorinated Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and ethyl carbonate (DEC); for example, application No. 201010561063.6 discloses that several sulfones are used as mixed solvent, and LiCoPO is improved after lithium bis (fluorooxalato) borate is added4High voltage charge-discharge cycle performance of the material battery; for example, Li et al disclose thiophene as an additive to Li/LiNi in electrolytes0.5Mn1.5O4The effect of the performance of the battery. The thiophene was investigated by SEM, TGA, XPS, CV and constant current charge and discharge, and it was found that thiophene was electropolymerized when the voltage reached 4.5V and the formed conductive polymer was covered at high voltageLiNi material0.5Mn1.5O4The particles surface, thereby inhibiting the dissolution of the transition metal during the cycling process, thereby improving the cycling stability of the battery.
Although the researchers can obviously improve the charge and discharge performance of the 5V lithium ion battery through research and experiments, as the requirement for high performance of the lithium ion battery is continuously improved, the students continuously expect that the lithium ion battery maintains high capacity and also needs to take into consideration the performances of continuous charge and discharge, internal resistance change, high-temperature storage, safety and the like.
Disclosure of Invention
The invention aims to provide an electrolyte for a lithium ion battery suitable for a 5V high-voltage anode material, and the electrolyte simultaneously solves the problems of cycle stability and safety performance of the battery under high voltage.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention aims to provide a lithium ion battery electrolyte, which comprises a solvent, lithium salt and an additive, wherein the additive comprises lithium difluorobis (malonate) phosphate and derivatives thereof shown in a structural formula (1) and/or lithium tetrafluoromalonate phosphate and derivatives thereof shown in a structural formula (2);
Figure BDA0001776239340000021
wherein Rx, Ry and Rz each independently represents an oxygen atom,OrR1, R2, R3, R4, R5, R6, R7 and R8 independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a haloalkyl group, an alkoxy group, a cyano group, an amino group or a nitro group, n is an integer of 1 to 12, and a and b are independently an integer of 1 to 6.
Preferably, the lithium difluorodimalonate phosphate and the derivatives thereof shown in the structural formula (1) are shown in the following structural formulaOne or more of the substances shown:
Figure BDA0001776239340000024
Figure BDA0001776239340000031
the lithium tetrafluoro-malonate phosphate and the derivative thereof shown in the structural formula (2) are one or more of the substances shown in the following structural formula:
Figure BDA0001776239340000032
Figure BDA0001776239340000033
several of the above compounds can be obtained according to a synthetic route analogous to that of the lithium difluorobis (oxalato) phosphate solution route mentioned under "CN 200980145463.4", for example
Figure BDA0001776239340000041
The compound is prepared by reacting lithium hexafluorophosphate and diethyl malonate in a non-aqueous solvent at a molar ratio of 1:2, then adding silicon tetrachloride in a molar ratio of 1:1 to react at 30-50 ℃, and finally purifying and drying, wherein the nuclear magnetic hydrogen spectrum data of the compound is shown in figure 4.
For another example
Figure BDA0001776239340000042
The compound is prepared by reacting lithium hexafluorophosphate and diethyl 2-fluoro malonate in a non-aqueous solvent at a molar ratio of 1:1, then adding silicon tetrachloride at a molar ratio of 1:1 to react at 30-50 ℃, and finally purifying and drying, wherein the nuclear magnetic hydrogen spectrum data of the compound is shown in figure 5.
Preferably, the total feeding mass of the lithium difluorobis (malonate) phosphate and the derivatives thereof shown in the structural formula (1) and the lithium tetrafluoromalonate phosphate and the derivatives thereof shown in the structural formula (2) is 0.05-5% of the total mass of the lithium ion battery electrolyte.
Further preferably, the total feeding mass of the lithium difluorobis (malonate) phosphate and the derivatives thereof shown in the structural formula (1) and the lithium tetrafluoromalonate phosphate and the derivatives thereof shown in the structural formula (2) is 0.1-2% of the total mass of the lithium ion battery electrolyte.
More preferably, the total feeding mass of the lithium difluorobis (malonate) phosphate and the derivatives thereof shown in the structural formula (1) and the lithium tetrafluoromalonate phosphate and the derivatives thereof shown in the structural formula (2) is 0.5-1.5% of the total mass of the lithium ion battery electrolyte.
Preferably, the solvent comprises a fluorinated solvent, and the fluorinated solvent is one or more of fluorinated carbonate, fluorinated carboxylate, fluorinated ether, fluorinated sulfone and fluorinated sulfoxide.
Wherein, the fluorinated solvent is one or more of fluoroethylene carbonate, difluoroethylene carbonate, trifluoroethyl carbonate, fluoroethylsulfone and tetrafluoroethyl tetrafluoropropyl ether.
More preferably, the mass of the fluorinated solvent added is 20% to 40% of the total mass of the lithium ion battery electrolyte.
Further preferably, the solvent further comprises other solvents, and the other solvents are one or more of carbonates, carboxylates, ethers, sulfones and sulfoxides.
Wherein the other solvent is one or more of dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, methyl ethyl carbonate, ethylene glycol dimethyl ether, r-butyrolactone, ethyl acetate, sulfolane, methyl ethyl sulfone and dimethyl sulfoxide.
More preferably, the addition mass of the other solvent is 50-60% of the total mass of the lithium ion battery electrolyte.
Preferably, the feeding mass of the solvent is 70-85% of the total mass of the lithium ion battery electrolyte.
More preferably, the feeding mass of the solvent is 80-85% of the total mass of the lithium ion battery electrolyte.
According to a specific and preferred embodiment, the solvent is a mixed solvent of fluoroethylene carbonate, diethyl carbonate and ethyl methyl carbonate, and the feeding mass ratio of fluoroethylene carbonate, diethyl carbonate and ethyl methyl carbonate is 1.2-1.8: 1: 1.5-2.
Preferably, the lithium salt is LiPF6、LiBF4、LiAsF6、LiClO4、LiBOB、LiDFOB、LiCF3SO3、LiC4F9SO3、Li(CF3SO2)2N、Li(C2F5SO2)2One or more of N, and further preferably LiPF6。
Preferably, the charging mass of the lithium salt is 10-25% of the total amount of the lithium ion battery electrolyte, and more preferably 10-15%.
Preferably, the additive also comprises other additives accounting for 0.5-5% of the total mass of the lithium ion battery electrolyte.
More preferably, the feeding mass of the other additives is 0.5-2% of the total mass of the lithium ion battery electrolyte
Further preferably, the other additive is one or more of a cyclic carbonate containing a double bond, a cyclic carbonate containing a halogen, an acid anhydride compound, a sulfonate, a sultone, a sulfate, a sulfite, a benzene compound, a fluorobenzene compound, a nitrile compound, a cyclic ether compound, a phosphazene compound, a phosphate, a boron compound, an amine compound, and a silicon-containing compound.
Wherein the other additives are vinylene carbonate, vinyl ethylene carbonate, succinic anhydride, phthalic anhydride, methylene methanedisulfonate, vinyl sulfate, vinyl sulfite, 1, 3-propane sultone, 1, 3-dioxane, biphenyl, cyclohexylbenzene, tert-butylbenzene, tert-amylbenzene, m-fluorotoluene, 3, 4-difluorotoluene, 4-bromo-2-fluorobenzene ether, p-fluorotoluene, p-xylene, 1, 2-dimethoxy-4-nitrobenzene, N-phenylmaleimide, pentafluoroanisole, 2, 5-di-tert-butyl, 1, 4-dimethoxybenzene, N-butylamine, methylamine, ethanolamine, N-dicyclohexylcarbodiimide, N-diethylamine trimethylsilane, hexamethyldisilazane, and the like, Hexaethyldisilazane, hexapropyldisilazane, triphenyl phosphate, adiponitrile, pimelonitrile, 1,3, 6-hexanetrinitrile, ethoxypentafluoropolyphosphazene, lithium dioxalate borate, lithium difluorooxalate borate, tris (trimethylsilane) phosphate.
According to a specific and preferred embodiment, the other additive is a combination of lithium difluoro-oxalato-borate, 1, 3-propane sultone, biphenyl and 1,3, 6-hexanetrinitrile, and the feeding mass ratio of the lithium difluoro-oxalato-borate, the 1, 3-propane sultone, the biphenyl and the 1,3, 6-hexanetrinitrile is 0.2-0.4: 0.9-1.2: 0.1-0.3: 1.
The invention also aims to provide a lithium ion battery, which comprises a positive electrode, a negative electrode and an electrolyte, wherein the electrolyte is the lithium ion battery electrolyte, and the active material of the positive electrode is LiMxMn2-xO4Or LiyMzPO4，LiMxMn2- xO4M in (B) is Cr, Co, Fe, Ni or Cu, LiyMzPO4Wherein M is Ni, Co or V, x is a number between 0.1 and 2, and y and z are independently integers of 1 to 5; the active material of the negative electrode is carbon material, lithium metal, lithium alloy, silicon material or other materials capable of reversibly forming lithium-containing compounds.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the invention, by adding the lithium difluorodimalonate phosphate and the derivatives thereof and/or the lithium tetrafluoromalonate phosphate and the derivatives thereof shown in the structural formula (2), effective passivation layers and SEI films can be respectively formed on the surfaces of the positive electrode and the negative electrode of the battery, so that the cycle life of the 5V high-voltage positive electrode material lithium ion battery under the higher voltage of 4.85V can be greatly prolonged, the bulging and the increase of internal resistance of the battery can be inhibited, and the safety test that the battery is not exploded and ignited by needling under the full-charge state is passed.
Drawings
FIG. 1 shows that S1 and S2 are at 3.0-7.0V (Li/Li)+) Lower broomCyclic voltammograms at a rate of 10 mV/s;
FIG. 2 shows application of S1 and S2 to LiNi0.5Mn1.5O4The first charge and discharge of the graphite full cell is d Q/d V picture (0-3V);
FIG. 3 shows application of S1 and S2 to LiNi0.5Mn1.5O4The first charge and discharge of the graphite full cell is d Q/d V picture (3.07-3.25V);
FIG. 4 is a drawing showing
Figure BDA0001776239340000071
Nuclear magnetic hydrogen spectrum of (a);
FIG. 5 is a drawing showing
Figure BDA0001776239340000072
Nuclear magnetic hydrogen spectrum diagram of (1).
Detailed Description
The present invention and its advantageous effects are further described below with reference to examples, but the present invention is not limited thereto.
Comparative example 1
The nonaqueous organic solvent is fluoroethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the three respectively account for 30 percent, 20 percent and 35 percent of the total mass of the electrolyte; the lithium salt being LiPF6And the lithium salt accounts for 12.5 percent of the total mass fraction of the electrolyte; the additive lithium difluoro oxalate borate accounts for 0.3 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 1 percent of the total mass of the electrolyte, the additive biphenyl accounts for 0.2 percent of the total mass of the electrolyte, and the additive 1,3, 6-hexanetricarbonitrile accounts for 1 percent of the total mass of the electrolyte.
Example 1
The nonaqueous organic solvent is fluoroethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the three respectively account for 30 percent, 20 percent and 34.5 percent of the total mass of the electrolyte; the lithium salt being LiPF6The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, the additive lithium difluoro-oxalato-borate accounts for 0.3 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 1 percent of the total mass of the electrolyte, and the additive biphenyl accounts for 1 percent of the total mass of the electrolyte0.2 percent of additive, 1 percent of 1,3, 6-hexanetricarbonitrile accounting for the total mass of the electrolyte and the additive
Figure BDA0001776239340000081
Accounting for 0.5 percent of the total mass of the electrolyte.
Example 2
The nonaqueous organic solvent is fluoroethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the fluoroethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate to the electrolyte is 30%, 20% and 34% respectively; the lithium salt being LiPF6And the lithium salt accounts for 12.5 percent of the total mass fraction of the electrolyte; the additive lithium difluoro oxalate borate accounts for 0.3 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 1 percent of the total mass of the electrolyte, the additive biphenyl accounts for 0.2 percent of the total mass of the electrolyte, the additive 1,3, 6-hexanetricarbonitrile accounts for 1 percent of the total mass of the electrolyte, and the additive
Figure BDA0001776239340000082
Accounting for 1 percent of the total mass of the electrolyte.
Example 3
The nonaqueous organic solvent is fluoroethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the three respectively account for 30 percent, 20 percent and 33.5 percent of the total mass of the electrolyte; the lithium salt being LiPF6And the lithium salt accounts for 12.5 percent of the total mass fraction of the electrolyte; the additive lithium difluoro oxalate borate accounts for 0.3 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 1 percent of the total mass of the electrolyte, the additive biphenyl accounts for 0.2 percent of the total mass of the electrolyte, the additive 1,3, 6-hexanetricarbonitrile accounts for 1 percent of the total mass of the electrolyte, and the additive
Figure BDA0001776239340000091
Accounting for 1.5 percent of the total mass of the electrolyte.
Example 4
The nonaqueous organic solvent is fluoroethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the three respectively account for 30 percent, 20 percent and 33 percent of the total mass of the electrolyte;the lithium salt being LiPF6And the lithium salt accounts for 12.5 percent of the total mass fraction of the electrolyte; the additive lithium difluoro oxalate borate accounts for 0.3 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 1 percent of the total mass of the electrolyte, the additive biphenyl accounts for 0.2 percent of the total mass of the electrolyte, the additive 1,3, 6-hexanetricarbonitrile accounts for 1 percent of the total mass of the electrolyte, and the additive
Figure BDA0001776239340000092
Accounting for 2 percent of the total mass of the electrolyte.
Example 5
The non-aqueous organic solvent is fluoroethylene carbonate, diethyl carbonate and methyl ethyl carbonate, which respectively account for 30 percent, 20 percent and 36.5 percent of the total mass of the electrolyte; the lithium salt being LiPF6And the lithium salt accounts for 12.5 percent of the total mass fraction of the electrolyte, the electrolyte is marked as S1, and 1 percent of the electrolyte is added on the basis of S1
Figure BDA0001776239340000093
As S2.
The results of cyclic voltammetry scanning tests of the two electrolytes show that the oxidation resistance of S2 is better than that of S1 as shown in figure 1;
injecting the above two electrolytes into LiNi0.5Mn1.5O4The d Q/d V test of the first charge and discharge in a graphite full cell, as shown in figures 2 and 3, shows that the additive forms obvious SEI on a negative electrode, and the additive can form obvious passive film on a positive electrode to protect the positive electrode.
Example 6
The nonaqueous organic solvent is fluoroethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the three respectively account for 30 percent, 20 percent and 34 percent of the total mass of the electrolyte; the lithium salt being LiPF6And the lithium salt accounts for 12.5 percent of the total mass fraction of the electrolyte; the additive lithium difluoro oxalate borate accounts for 0.3 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 1 percent of the total mass of the electrolyte, and the additive biphenyl accounts for 0 percent of the total mass of the electrolyte.2 percent of additive 1,3, 6-hexanetricarbonitrile accounting for 1 percent of the total mass of the electrolyte, and the additive
Figure BDA0001776239340000101
Accounting for 1 percent of the total mass of the electrolyte.
Example 7
The nonaqueous organic solvent is fluoroethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the three respectively account for 30 percent, 20 percent and 34 percent of the total mass of the electrolyte; the lithium salt being LiPF6And the lithium salt accounts for 12.5 percent of the total mass fraction of the electrolyte; the additive lithium difluoro oxalate borate accounts for 0.3 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 1 percent of the total mass of the electrolyte, the additive biphenyl accounts for 0.2 percent of the total mass of the electrolyte, the additive 1,3, 6-hexanetricarbonitrile accounts for 1 percent of the total mass of the electrolyte, and the additive
Figure BDA0001776239340000111
Accounting for 1 percent of the total mass of the electrolyte.
Example 8
The nonaqueous organic solvent is fluoroethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the three respectively account for 30 percent, 20 percent and 34 percent of the total mass of the electrolyte; the lithium salt being LiPF6And the lithium salt accounts for 12.5 percent of the total mass fraction of the electrolyte; the additive lithium difluoro oxalate borate accounts for 0.3 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 1 percent of the total mass of the electrolyte, the additive biphenyl accounts for 0.2 percent of the total mass of the electrolyte, the additive 1,3, 6-hexanetricarbonitrile accounts for 1 percent of the total mass of the electrolyte, and the additive
Figure BDA0001776239340000112
Accounting for 1 percent of the total mass of the electrolyte.
Example 9
The nonaqueous organic solvent is fluoroethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the nonaqueous organic solvent, the fluoroethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate respectively account for 30 percent, 20 percent and 34 percent of the total mass ratio of the electrolyte; lithium saltIs LiPF6And the lithium salt accounts for 12.5 percent of the total mass fraction of the electrolyte; the additive lithium difluoro oxalate borate accounts for 0.3 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 1 percent of the total mass of the electrolyte, the additive biphenyl accounts for 0.2 percent of the total mass of the electrolyte, the additive 1,3, 6-hexanetricarbonitrile accounts for 1 percent of the total mass of the electrolyte, and the additive
Figure BDA0001776239340000121
Accounting for 1 percent of the total mass of the electrolyte.
Example 10
The nonaqueous organic solvent is fluoroethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the three respectively account for 30 percent, 20 percent and 34 percent of the total mass of the electrolyte; the lithium salt being LiPF6And the lithium salt accounts for 12.5 percent of the total mass fraction of the electrolyte; the additive lithium difluoro oxalate borate accounts for 0.3 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 1 percent of the total mass of the electrolyte, the additive biphenyl accounts for 0.2 percent of the total mass of the electrolyte, the additive 1,3, 6-hexanetricarbonitrile accounts for 1 percent of the total mass of the electrolyte, and the additive
Figure BDA0001776239340000122
Accounting for 1 percent of the total mass of the electrolyte.
Example 11
The nonaqueous organic solvent is fluoroethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the three respectively account for 30 percent, 20 percent and 34 percent of the total mass of the electrolyte; the lithium salt being LiPF6And the lithium salt accounts for 12.5 percent of the total mass fraction of the electrolyte; the additive lithium difluoro oxalate borate accounts for 0.3 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 1 percent of the total mass of the electrolyte, the additive biphenyl accounts for 0.2 percent of the total mass of the electrolyte, the additive 1,3, 6-hexanetricarbonitrile accounts for 1 percent of the total mass of the electrolyte, and the additive
Figure BDA0001776239340000131
Accounting for 1 percent of the total mass of the electrolyte.
Example 12
The nonaqueous organic solvent is fluoroethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the three respectively account for 30 percent, 20 percent and 34 percent of the total mass of the electrolyte; the lithium salt being LiPF6And the lithium salt accounts for 12.5 percent of the total mass fraction of the electrolyte; the additive lithium difluoro oxalate borate accounts for 0.3 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 1 percent of the total mass of the electrolyte, the additive biphenyl accounts for 0.2 percent of the total mass of the electrolyte, the additive 1,3, 6-hexanetricarbonitrile accounts for 1 percent of the total mass of the electrolyte, and the additive
Figure BDA0001776239340000132
0.5 percent of additive accounting for the total mass of the electrolyte
Figure BDA0001776239340000133
Accounting for 0.5 percent of the total mass of the electrolyte.
Results of the experiment
The electrolytes of comparative example 1 and examples 1 to 4 and examples 6 to 12 were injected into LiNi of the same lot0.5Mn1.5O4And Li3V2PO4The test result shows that the high-voltage cycle and safety performance of the battery in the environment of normal temperature and high temperature of 85 ℃ are tested in the aluminum-shell battery with the standard capacity of 1Ah and the graphite as the cathode active material.
LiNi0.5Mn1.5O4The data for the cell cycled at 4.85V at ambient temperature and left at 85 ℃ for 4H were compared as follows:
Figure BDA0001776239340000141
Li3V2PO4the data for the cell cycled at 4.9V at ambient temperature and left at 85 ℃ for 4H were compared as follows:
Figure BDA0001776239340000151
LiNi0.5Mn1.5O4the battery safety test data is compared as follows:
4.85V full electrical acupuncture condition
Comparative example 1 Smoke-generating explosion
Example 1 Smoke-generating and non-explosion
Example 2 No smoke and explosion
Example 3 Smoke-generating and non-explosion
Example 4 Smoke-generating and non-explosion
Example 6 No smoke and explosion
Example 7 No smoke and explosion
Example 8 No smoke and explosion
Example 9 No smoke and explosion
Example 10 No smoke and explosion
Example 11 No smoke and explosion
Example 12 No smoke and explosion
Li3V2PO4The battery safety test data is compared as follows:
Figure BDA0001776239340000152
as can be seen from the above table, the examples of the present invention are significantly superior to the batteries prepared in the comparative examples in terms of both the normal temperature cycle, the high temperature shelf life and the safety.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.

Claims (10)

1. The lithium ion battery electrolyte comprises a solvent, lithium salt and an additive, and is characterized in that: the additive comprises lithium difluorobis (malonate) phosphate and derivatives thereof shown in a structural formula (1) and/or lithium tetrafluoromalonate phosphate and derivatives thereof shown in a structural formula (2);
Figure FDA0001776239330000011
wherein Rx, Ry and Rz each independently represents an oxygen atom,
Figure FDA0001776239330000012
R1, R2, R3, R4, R5, R6, R7 and R8 independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a haloalkyl group, an alkoxy group, a cyano group, an amino group or a nitro group, n is an integer of 1 to 12, and a and b are independently an integer of 1 to 6.
2. The lithium ion battery electrolyte of claim 1, wherein: the lithium difluorodimalonate phosphate and the derivative thereof shown in the structural formula (1) are one or more of the substances shown in the following structural formula:
the lithium tetrafluoro-malonate phosphate and the derivative thereof shown in the structural formula (2) are one or more of the substances shown in the following structural formula:
Figure FDA0001776239330000021
Figure FDA0001776239330000022
3. the lithium ion battery electrolyte of claim 1 or 2, wherein: the total feeding mass of the lithium difluorobis (malonate) phosphate and the derivatives thereof shown in the structural formula (1) and the total feeding mass of the lithium tetrafluoromalonate phosphate and the derivatives thereof shown in the structural formula (2) is 0.05-5% of the total mass of the lithium ion battery electrolyte.
4. The lithium ion battery electrolyte of claim 3, wherein: the total feeding mass of the lithium difluorobis (malonate) phosphate and the derivatives thereof shown in the structural formula (1) and the total feeding mass of the lithium tetrafluoromalonate phosphate and the derivatives thereof shown in the structural formula (2) is 0.1-2% of the total mass of the lithium ion battery electrolyte.
5. The lithium ion battery electrolyte of claim 1 or 2, wherein: the solvent comprises a fluorinated solvent, and the fluorinated solvent is one or more of fluorinated carbonate, fluorinated carboxylate, fluorinated ether, fluorinated sulfone and fluorinated sulfoxide.
6. The lithium ion battery electrolyte of claim 5, wherein: the solvent also comprises other solvents, and the other solvents are one or more of carbonate, carboxylate, ether, sulfone and sulfoxide.
7. The lithium ion battery electrolyte of claim 1 or 2, wherein: the feeding mass of the solvent is 70-85% of the total mass of the lithium ion battery electrolyte.
8. The lithium ion battery electrolyte of claim 1 or 2, wherein: the lithium salt is LiPF6、LiBF4、LiAsF6、LiClO4、LiBOB、LiDFOB、LiCF3SO3、LiC4F9SO3、Li(CF3SO2)2N、Li(C2F5SO2)2And N, wherein the charging mass of the lithium salt is 10-25% of the total mass of the lithium ion battery electrolyte.
9. The lithium ion battery electrolyte of claim 1 or 2, wherein: the additive also comprises other additives accounting for 0.5-5% of the total mass of the lithium ion battery electrolyte, wherein the other additives are one or more of double-bond-containing cyclic carbonate, halogen-containing cyclic carbonate, an anhydride compound, sulfonate, sultone, sulfate, sulfite, a benzene compound, a fluorobenzene compound, a nitrile compound, a cyclic ether compound, a phosphazene compound, phosphate, a boron compound, an amine compound and a silicon-containing compound.
10. A lithium ion battery comprises a positive electrode, a negative electrode and electrolyte, and is characterized in that: the electrolyte is the lithium ion battery electrolyte as defined in any one of claims 1 to 9, and the active material of the positive electrode is LiMxMn2-xO4Or LiyMzPO4，LiMxMn2-xO4M in (B) is Cr, Co, Fe, Ni or Cu, LiyMzPO4Wherein M is Ni, Co or V, x is a number between 0.1 and 2, and y and z are independently integers of 1 to 5; the active material of the negative electrode is carbon material, lithium metal, lithium alloy, silicon material or other materials capable of reversibly forming lithium-containing compounds.
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