CN113991178A - Non-aqueous electrolyte of lithium ion battery and application thereof - Google Patents
Non-aqueous electrolyte of lithium ion battery and application thereof Download PDFInfo
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- 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
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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- 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
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Abstract
The invention provides a lithium ion battery non-aqueous electrolyte and application thereof. The non-aqueous electrolyte of the lithium ion battery comprises an electrolyte, a non-aqueous solvent and an additive, wherein the additive comprises a first compound and a cyclic ester additive. The lithium ion battery non-aqueous electrolyte provided by the invention contains the first compound and the cyclic ester additive, so that a stable SEI film can be formed on the surfaces of the positive and negative electrode materials, and the high-temperature storage performance and the gas generation inhibition of the lithium ion battery are improved.
Description
Technical Field
The invention belongs to the field of batteries, and particularly relates to a non-aqueous electrolyte of a lithium ion battery and application thereof.
Background
The lithium ion battery has the advantages of high energy density, high working voltage, long cycle life, no memory effect and the like, is one of main energy storage devices of the conventional portable electronic equipment, and simultaneously shows good performance in the application fields of electric vehicles, intelligent Internet of things and the like.
To further meet the growing application demands, lithium ion batteries also need to have higher energy densities. At present, the improvement of the energy density of a lithium ion battery in the prior art is mainly divided into two ways: one way is to adopt a positive electrode material with high content of nickel element to improve specific capacity; another way is to increase the charge cutoff voltage of the lithium ion battery. However, the solutions disclosed in the prior art all have an adverse effect on the electrolyte. On one hand, the stability of the cathode material is reduced due to too high content of nickel element, and the unstable trivalent nickel ions can cause the side reaction of the electrolyte on the cathode side through oxidative decomposition; on the other hand, simply increasing the charge cut-off voltage of the battery raises the reaction potential of the positive electrode material, and causes a series of problems such as battery gassing and increase in interface impedance accompanied by the oxidative decomposition process of the electrolyte. In summary, the above shows that more stringent requirements are placed on the electrolyte material.
In view of the above, there is a need in the art to develop and provide a Solid Electrolyte Interface (SEI) that can solve the above problems and is stable, not only can inhibit the Electrolyte from continuously generating side reactions with the positive electrode and the negative electrode, but also can improve the high-temperature storage performance and safety performance of the lithium ion secondary battery.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a lithium ion battery nonaqueous electrolyte and application thereof. The lithium ion battery non-aqueous electrolyte provided by the invention contains the first compound and the cyclic ester additive, so that a stable SEI film can be formed on the surfaces of the positive and negative electrode materials, and the high-temperature storage performance and the gas generation inhibition of the lithium ion battery are improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a nonaqueous electrolyte for a lithium ion battery, including an electrolyte, a nonaqueous solvent, and an additive, where the additive includes a first compound having a structure represented by formula 1 and a cyclic ester additive:
wherein R is1、R2、R3And R4Independently selected from-O-CH ═ CH2Or an ethynyl group.
On one hand, the first compound in the additive provided by the invention has a higher electron cloud density of double bonds due to a stronger electron-pushing effect of oxygen atoms, and is easier to generate oxidative polymerization reaction on the anode under the regulation and control of voltage, so that a multidimensional network structure with good flexibility is formed; on the other hand, in the first compound, carbon atoms in the ethynyl are sp hybridized, and the electron withdrawing property of the alkynyl is stronger after the proportion of the s orbital component in the hybridized orbitals is increased, so that reduction polymerization reaction is easy to occur on the negative electrode, and a multidimensional network with certain rigidity is formed. In conclusion, the first compound and the cyclic ester additive in the electrolyte provided by the invention are compounded, so that the formation of a compact SEI film at the interface of the positive electrode and the interface of the negative electrode can be effectively promoted, and the high-temperature storage performance of the battery can be improved.
Preferably, the first compound includes a second compound having a structure shown in formula 2 or a third compound having a structure shown in formula 3;
preferably, the mass percentage of the first compound in the lithium ion battery nonaqueous electrolyte is 0.05% to 5%, for example, 0.05%, 0.1%, 0.5%, 1%, 2% or 5%, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the content of the cyclic ester additive in the non-aqueous electrolyte of the lithium ion battery is 0.05% to 20% by mass, for example, 0.05%, 0.5%, 1%, 5%, 10% or 20% by mass, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the cyclic ester additive in the non-aqueous electrolyte solution of the lithium ion battery includes any one or a combination of at least two of a cyclic carbonate additive, a cyclic sultone additive or a cyclic sulfate additive, and may be, for example, a cyclic carbonate additive, a cyclic sultone additive and a cyclic sulfate additive, a cyclic carbonate additive and a cyclic sultone additive, a cyclic carbonate additive and a cyclic sulfate additive or a cyclic sultone additive and a cyclic sulfate, but is not limited to the listed species, and other species not listed within the scope of the cyclic ester additive are also applicable.
Preferably, the cyclic carbonate additive includes any one or a combination of at least two of vinylene carbonate, fluoroethylene carbonate or ethylene-ethylene carbonate, such as vinylene carbonate, fluoroethylene carbonate and ethylene-ethylene carbonate, fluoroethylene carbonate and vinylene carbonate or ethylene-ethylene carbonate, but not limited to the listed species, and other species not listed within the scope of the cyclic carbonate additive are also applicable.
Preferably, the cyclic sultone additive comprises any one or two of 1, 3-propane sultone and 1, 3-propylene sultone, such as 1, 3-propane sultone and 1, 3-propylene sultone, 1, 3-propane sultone or 1, 3-propylene sultone.
Preferably, the cyclic sulfate-based additive includes any one of or a combination of at least two of vinyl sulfate and propylene sulfate, and may be, for example, vinyl sulfate and propylene sulfate, vinyl sulfate or propylene sulfate.
Preferably, the electrolyte is a lithium salt.
Preferably, the lithium salt comprises lithium hexafluorophosphate.
Preferably, the concentration of lithium hexafluorophosphate in the non-aqueous electrolyte of the lithium ion battery is 0.5mol/L to 2mol/L, for example, 0.5mol/L, 1mol/L, 1.5mol/L or 2mol/L, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the additive further comprises a lithium salt additive.
Preferably, the lithium salt additive includes any one or a combination of at least two of lithium bis (oxalate) difluorophosphate, lithium difluoro (oxalate) borate, lithium bis (fluorosulfonyl) imide or lithium bis (trifluoromethyl) sulfonyl imide, such as lithium bis (oxalate) difluorophosphate and lithium difluorophosphate, lithium difluoro (oxalate) borate or lithium bis (trifluoromethanesulfonyl) imide, but not limited to the enumerated species, and other species not enumerated within the scope of the lithium salt additive are equally applicable.
Preferably, the lithium salt additive is contained in the lithium ion battery nonaqueous electrolyte in an amount of 0.05% to 20% by mass, for example, 0.05%, 0.5%, 1%, 5%, 10% or 20% by mass, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the non-aqueous solvent includes any one or a combination of at least two of ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene carbonate or diethyl carbonate, such as ethylene carbonate and dimethyl carbonate, ethyl methyl carbonate and propylene carbonate or diethyl carbonate, but is not limited to the listed species, and other species not listed in the non-aqueous solvent are also applicable.
Preferably, the content of the nonaqueous solvent in the nonaqueous electrolyte solution of the lithium ion battery is 60% to 85% by mass, for example, 60%, 65%, 70%, 75%, 80% or 85%, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
In a second aspect, the invention provides a lithium ion battery, which comprises the lithium ion battery nonaqueous electrolyte solution of the first aspect.
Preferably, the lithium ion battery further comprises a positive electrode current collector, a positive electrode active material coated on the positive electrode current collector, a negative electrode active material coated on the negative electrode current collector, and a separator.
Preferably, the positive active material includes any one or a combination of at least two of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt manganese oxide, or lithium nickel cobalt aluminum oxide, and may be, for example, lithium cobalt oxide and lithium nickel oxide, lithium manganese oxide and lithium nickel manganese oxide, lithium nickel cobalt manganese oxide, or lithium nickel cobalt aluminum oxide, but is not limited to the listed species, and other species not listed in the scope of the positive active material are also applicable.
Preferably, the negative electrode active material includes any one or a combination of at least two of soft carbon, hard carbon, artificial graphite, natural graphite, silicon oxide, silicon carbon compound or lithium titanate, for example, the soft carbon and hard carbon, artificial graphite and natural graphite, silicon oxide, silicon carbon compound or lithium titanate may be used, but not limited to the listed species, and other species not listed in the scope of the negative electrode active material may be equally applicable.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a lithium ion battery non-aqueous electrolyte which can inhibit the reaction of the electrolyte and a positive electrode/a negative electrode under a high-temperature state so as to improve the high-temperature storage performance of a lithium ion battery. The second compound additive is adopted to enhance the electron cloud density of the substituent group, which is beneficial to the oxidative polymerization reaction of the substituent group, so that the chain growth reaction is generated and a compact and uniform SEI film is formed on the surface of the anode material; the third compound is favorable for reduction polymerization reaction due to the electron-deficient characteristic of acetylene groups, so that an SEI film is formed on the surface of the negative electrode material; under the synergistic effect of the positive electrode and the negative electrode, the surfaces of the positive electrode and the negative electrode are well protected, so that the high-temperature storage performance of the battery is greatly improved.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
In the prior art, the energy density of the lithium ion battery is improved by adopting a high-content nickel element anode material and improving the charge cut-off voltage. However, the solutions disclosed in the prior art all have adverse effects on the electrolyte, such as side reactions, gas generation and increased interfacial resistance.
In order to solve the technical problems, the invention provides a lithium ion battery nonaqueous electrolyte and application thereof.
An embodiment of the invention provides a lithium ion battery nonaqueous electrolyte, which includes an electrolyte, a nonaqueous solvent, and an additive, wherein the additive includes a first compound having a structure shown in formula 1 and a cyclic ester additive:
wherein R is1、R2、R3And R4Independently selected from-O-CH ═ CH2Or an ethynyl group.
The first compound additive adopted by the invention can enhance (selecting-O-CH ═ CH)2Substituent group) or weakening (selecting acetylene substituent group) the electron cloud density of the substituent group, which is beneficial to the oxidation or reduction polymerization reaction of the substituent group, so that the chain growth reaction is generated, a compact and uniform SEI film is formed on the surface of the electrode material, and the SEI film is compounded with the cyclic ester additive for use, thereby optimizing the high-temperature storage performance of the battery.
In some embodiments, the first compound comprises a second compound having a structure represented by formula 2 or a third compound having a structure represented by formula 3:
in some embodiments, the mass percentage of the first compound in the lithium ion battery nonaqueous electrolyte is 0.05% to 5%.
In some embodiments, the content of the cyclic ester additive in the nonaqueous electrolyte solution of the lithium ion battery is 0.05% to 20% by mass.
In some embodiments, the cyclic ester additive in the nonaqueous electrolyte solution of the lithium ion battery includes any one of or a combination of at least two of a cyclic carbonate additive, a cyclic sultone additive, or a cyclic sulfate additive.
In some embodiments, the cyclic carbonate-based additive includes any one of vinylene carbonate, fluoroethylene carbonate, or ethylene carbonate, or a combination of at least two thereof.
In some embodiments, the cyclic sultone-based additive comprises any one of 1, 3-propane sultone, 1, 3-propene sultone, or a combination of both.
In some embodiments, the cyclic sulfate-based additive includes any one of vinyl sulfate, propylene sulfate, or a combination of at least two thereof.
In some embodiments, the electrolyte is a lithium salt.
In some embodiments, the lithium salt comprises lithium hexafluorophosphate.
In some embodiments, the concentration of lithium hexafluorophosphate in the lithium ion battery nonaqueous electrolyte is 0.5 to 2 mol/L.
In some embodiments, the additive further comprises a lithium salt additive.
In some embodiments, the lithium salt additive comprises any one of or a combination of at least two of lithium bis (oxalato) difluorophosphate, lithium difluorooxalato borate, lithium bis (fluorosulfonyl) imide, or lithium bis (trifluoromethylsulfonyl) imide.
In some embodiments, the lithium salt additive is present in the lithium ion battery nonaqueous electrolyte in an amount of 0.05% to 20% by mass.
In some embodiments, the non-aqueous solvent comprises any one of ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene carbonate, or diethyl carbonate, or a combination of at least two thereof.
In some embodiments, the nonaqueous solvent in the nonaqueous electrolyte solution of the lithium ion battery is 60 to 85 mass percent.
In one embodiment, a lithium ion battery comprising the lithium ion battery non-aqueous electrolyte is provided.
In one embodiment, the lithium ion battery further includes a positive electrode current collector and a positive electrode active material coated on the positive electrode current collector, a negative electrode current collector and a negative electrode active material coated on the negative electrode current collector, and a separator.
In one embodiment, the positive active material includes any one of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt manganese oxide, or lithium nickel cobalt aluminum oxide, or a combination of at least two thereof.
In one embodiment, the negative active material includes any one of soft carbon, hard carbon, artificial graphite, natural graphite, silicon oxy compound, silicon carbon compound, or lithium titanate, or a combination of at least two thereof.
Example 1
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises 2.5 mass percent of tetraenylsiloxane, 2.5 mass percent of vinylene carbonate, 2.5 mass percent of 1, 3-propane sultone and 5 mass percent of ethylene sulfate as additives, wherein lithium salt comprises 1mol/L lithium hexafluorophosphate, 2.5 mass percent of lithium difluorophosphate, 2.5 mass percent of lithium difluorosulfonimide and 5 mass percent of lithium difluorophosphate, and the balance is a nonaqueous solvent, wherein the nonaqueous solvent consists of ethylene carbonate, methyl ethyl carbonate and diethyl carbonate in a mass ratio of 3:5: 2.
The preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was prepared in a glove box with a nitrogen content of 99.999%, an actual oxygen content of 0.1ppm and a moisture content of 0.1 ppm. Uniformly mixing ethylene carbonate, ethyl methyl carbonate and a diethyl carbonate battery-grade organic solvent in a mass ratio of 3:5:2 by taking the total mass of the nonaqueous electrolyte as 100%, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding 2.5% by mass of tetraenylsiloxane, 2.5% by mass of vinylene carbonate, 2.5% by mass of 1, 3-propane sultone and 5% by mass of ethylene sulfate, and adding 2.5% by mass of lithium difluorophosphate, 2.5% by mass of lithium difluorosulfonimide and 5% by mass of lithium difluorophosphate to make the concentration of the lithium hexafluorophosphate be 1mol/L, thereby preparing the lithium ion battery nonaqueous electrolyte.
The preparation method of the lithium ion battery comprises the following steps:
LiNi as positive electrode active material0.8Co0.1Mn0.1O2The conductive agent acetylene black and the adhesive polyvinylidene fluoride are fully stirred and uniformly mixed in an N-methyl pyrrolidone solvent system according to the mass ratio of 95:3:2, coated on an aluminum foil, dried and cold-pressed to obtain the positive pole piece, and the compaction density of the positive pole piece is 3.5g/cm3。
Fully stirring and uniformly mixing the negative active material graphite, the conductive agent acetylene black, the binder styrene butadiene rubber and the thickener carboxymethylcellulose sodium in a deionized water solvent system according to the mass ratio of 96:2:1:1, coating the mixture on a copper foil, drying and cold pressing to obtain a negative pole piece, wherein the compaction density of the negative pole piece is 1.65g/cm3。
Polyethylene with the thickness of 9 mu m is taken as a base film, and a nano aluminum oxide coating with the thickness of 3 mu m is coated on the base film to obtain the diaphragm.
And stacking the positive pole piece, the diaphragm and the negative pole piece in sequence, so that the diaphragm is positioned between the positive pole piece and the negative pole piece to play an isolating role, and stacking the pieces to obtain the bare cell.
And (2) filling the bare cell into an aluminum plastic film, baking at 80 ℃ to remove water, injecting corresponding electrolyte, sealing, standing, hot-cold pressing, forming, clamping, capacity grading and other procedures to obtain the finished product of the flexibly-packaged lithium ion secondary battery.
Example 2
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises 0.05% of tetraenylsiloxane, 0.025% of vinylene carbonate and 0.025% of 1, 3-propane sultone by mass percentage based on 100% of the total mass of the nonaqueous electrolyte, lithium salt is lithium hexafluorophosphate with the concentration of 0.5mol/L, 5% of lithium difluorophosphate, 5% of lithium difluorosulfonimide and 10% of lithium difluorophosphate by mass percentage, and the balance is a nonaqueous solvent, wherein the nonaqueous solvent is composed of ethylene carbonate, ethyl methyl carbonate and diethyl carbonate in a mass ratio of 3:5: 2.
The preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was prepared in a glove box with a nitrogen content of 99.999%, an actual oxygen content of 0.1ppm and a moisture content of 0.1 ppm. Uniformly mixing ethylene carbonate, ethyl methyl carbonate and a diethyl carbonate battery grade organic solvent in a mass ratio of 3:5:2 by taking the total mass of the non-aqueous electrolyte as 100%, adding fully dried lithium hexafluorophosphate into the non-aqueous solvent, adding 0.05% of tetraenylsiloxane, 0.025% of vinylene carbonate and 0.025% of 1, 3-propane sultone in mass percentage, and then adding 5% of lithium difluorophosphate, 5% of lithium difluorosulfonimide and 10% of lithium difluorophosphate in mass percentage to enable the concentration of the lithium hexafluorophosphate to be 0.5mol/L, so as to prepare the lithium ion battery non-aqueous electrolyte.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 3
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises 5 mass percent of tetraenylsiloxane, 5 mass percent of vinylene carbonate, 10 mass percent of 1, 3-propane sultone and 5 mass percent of vinyl sulfate as additives, lithium salt is 2mol/L lithium hexafluorophosphate, 0.025 mass percent of lithium difluorophosphate and 0.025 mass percent of lithium difluorosulfonimide, and the balance is a nonaqueous solvent, wherein the nonaqueous solvent is composed of vinyl carbonate, methyl ethyl carbonate and diethyl carbonate according to the mass ratio of 3:5: 2.
The preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was prepared in a glove box with a nitrogen content of 99.999%, an actual oxygen content of 0.1ppm and a moisture content of 0.1 ppm. Uniformly mixing ethylene carbonate, ethyl methyl carbonate and a diethyl carbonate battery-grade organic solvent in a mass ratio of 3:5:2 by taking the total mass of the non-aqueous electrolyte as 100%, adding fully dried lithium hexafluorophosphate into the non-aqueous solvent, adding 5% of tetraenylsiloxane, 5% of vinylene carbonate, 10% of 1, 3-propane sultone and 5% of vinyl sulfate in percentage by mass, and then adding 0.025% of lithium difluorophosphate and 0.025% of lithium difluorosulfonimide in percentage by mass to enable the concentration of the lithium hexafluorophosphate to be 2mol/L, thereby preparing the lithium ion battery non-aqueous electrolyte.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 4
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises 0.05% of tetraenylsiloxane, 1% of ethylene sulfate, 0.5% of vinylene carbonate and 1% of 1, 3-propane sultone by mass percentage based on 100% of the total mass of the nonaqueous electrolyte, lithium salt comprises lithium hexafluorophosphate with the concentration of 1mol/L, 0.8% of lithium difluorophosphate, 0.5% of lithium difluorosulfonimide and 0.5% of lithium difluorophosphate by mass percentage based on the total mass of the nonaqueous electrolyte, and the balance is a nonaqueous solvent which is composed of ethylene carbonate, ethyl methyl carbonate and diethyl carbonate in a mass ratio of 3:5: 2.
The preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was prepared in a glove box with a nitrogen content of 99.999%, an actual oxygen content of 0.1ppm and a moisture content of 0.1 ppm. Uniformly mixing ethylene carbonate, ethyl methyl carbonate and a diethyl carbonate battery-grade organic solvent in a mass ratio of 3:5:2 by taking the total mass of the nonaqueous electrolyte as 100%, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding 0.05% of tetraenylsiloxane, 1% of ethylene sulfate, 0.5% of vinylene carbonate and 1% of 1, 3-propane sultone in percentage by mass, respectively, adding 0.8% of lithium difluorophosphate, 0.5% of lithium difluorosulfonimide and 0.5% of lithium difluorophosphate in percentage by mass, so that the concentration of the lithium hexafluorophosphate is 1mol/L, and preparing the lithium ion battery nonaqueous electrolyte.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 5
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises 0.2 mass percent of tetraenylsiloxane, 1 mass percent of ethylene sulfate, 0.5 mass percent of vinylene carbonate and 1 mass percent of 1, 3-propane sultone additive, wherein the lithium salt comprises lithium hexafluorophosphate with the concentration of 1mol/L, 0.8 mass percent of lithium difluorophosphate, 0.5 mass percent of lithium bifluorosulfonyl imide and 0.5 mass percent of lithium bifluorosulfonate, and the balance is a nonaqueous solvent, and the nonaqueous solvent consists of ethylene carbonate, ethyl methyl carbonate and diethyl carbonate in a mass ratio of 3:5:2, wherein the total mass of the nonaqueous electrolyte is 100%.
The preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was prepared in a glove box with a nitrogen content of 99.999%, an actual oxygen content of 0.1ppm and a moisture content of 0.1 ppm. Uniformly mixing ethylene carbonate, ethyl methyl carbonate and a diethyl carbonate battery-grade organic solvent in a mass ratio of 3:5:2 by taking the total mass of the nonaqueous electrolyte as 100%, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding 0.2% by mass of tetraenylsiloxane, 1% by mass of ethylene sulfate, 0.5% by mass of vinylene carbonate and 1% by mass of 1, 3-propane sultone respectively, adding 0.8% by mass of lithium difluorophosphate, 0.5% by mass of lithium difluorosulfonimide and 0.5% by mass of lithium difluorophosphate respectively, and enabling the concentration of the lithium hexafluorophosphate to be 1mol/L to prepare the lithium ion battery nonaqueous electrolyte.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 6
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises 1% of tetraenylsiloxane, 1% of ethylene sulfate, 0.5% of vinylene carbonate and 1% of 1, 3-propane sultone by mass percentage based on 100% of the total mass of the nonaqueous electrolyte, lithium salt comprises lithium hexafluorophosphate with the concentration of 1mol/L, 0.8% of lithium difluorophosphate, 0.5% of lithium difluorosulfonimide and 0.5% of lithium difluorophosphate by mass percentage, and the balance is a nonaqueous solvent, wherein the nonaqueous solvent is composed of ethylene carbonate, ethyl methyl carbonate and diethyl carbonate in a mass ratio of 3:5: 2.
The preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was prepared in a glove box with a nitrogen content of 99.999%, an actual oxygen content of 0.1ppm and a moisture content of 0.1 ppm. Uniformly mixing ethylene carbonate, ethyl methyl carbonate and a diethyl carbonate battery-grade organic solvent in a mass ratio of 3:5:2 by taking the total mass of the nonaqueous electrolyte as 100%, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding 1% by mass of tetraenylsiloxane, 1% by mass of ethylene sulfate, 0.5% by mass of vinylene carbonate and 1% by mass of 1, 3-propane sultone respectively, adding 0.8% by mass of lithium difluorophosphate, 0.5% by mass of lithium difluorosulfonimide and 0.5% by mass of lithium difluorophosphate respectively, and enabling the concentration of the lithium hexafluorophosphate to be 1mol/L to prepare the lithium ion battery nonaqueous electrolyte.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 7
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises 2.5 mass percent of tetraenylsiloxane, 1 mass percent of ethylene sulfate, 0.5 mass percent of vinylene carbonate and 1 mass percent of 1, 3-propane sultone additive, wherein the lithium salt comprises lithium hexafluorophosphate with the concentration of 1mol/L, 0.8 mass percent of lithium difluorophosphate, 0.5 mass percent of lithium bifluorosulfonyl imide and 0.5 mass percent of lithium bifluorodifluorophosphate, and the balance is a nonaqueous solvent, and the nonaqueous solvent consists of ethylene carbonate, ethyl methyl carbonate and diethyl carbonate in a mass ratio of 3:5:2, wherein the total mass of the nonaqueous electrolyte is 100%.
The preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was prepared in a glove box with a nitrogen content of 99.999%, an actual oxygen content of 0.1ppm and a moisture content of 0.1 ppm. Uniformly mixing ethylene carbonate, ethyl methyl carbonate and a diethyl carbonate battery-grade organic solvent in a mass ratio of 3:5:2 by taking the total mass of the nonaqueous electrolyte as 100%, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding 2.5% by mass of tetraenylsiloxane, 1% by mass of ethylene sulfate, 0.5% by mass of vinylene carbonate and 1% by mass of 1, 3-propane sultone respectively, adding 0.8% by mass of lithium difluorophosphate, 0.5% by mass of lithium difluorosulfonimide and 0.5% by mass of lithium difluorophosphate respectively, and enabling the concentration of the lithium hexafluorophosphate to be 1mol/L to prepare the lithium ion battery nonaqueous electrolyte.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 8
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises 0.05% of tetraacetylsilane, 1% of ethylene sulfate, 0.5% of vinylene carbonate and 1% of 1, 3-propane sultone by mass percentage based on 100% of the total mass of the nonaqueous electrolyte, lithium salt comprises lithium hexafluorophosphate with the concentration of 1mol/L, and lithium difluorophosphate with the mass percentage of 0.8%, lithium difluorosulfonimide with the mass percentage of 0.5% and lithium difluorophosphate with the mass percentage of 0.5% by mass, and the balance is a nonaqueous solvent, wherein the nonaqueous solvent is composed of ethylene carbonate, ethyl methyl carbonate and diethyl carbonate in a mass ratio of 3:5: 2.
The preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was prepared in a glove box with a nitrogen content of 99.999%, an actual oxygen content of 0.1ppm and a moisture content of 0.1 ppm. Uniformly mixing ethylene carbonate, ethyl methyl carbonate and a diethyl carbonate battery-grade organic solvent in a mass ratio of 3:5:2 by taking the total mass of the nonaqueous electrolyte as 100%, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding 0.05% by mass of tetraacetylsilane, 1% by mass of ethylene sulfate, 0.5% by mass of vinylene carbonate and 1% by mass of 1, 3-propane sultone, and adding 0.8% by mass of lithium difluorophosphate, 0.5% by mass of lithium difluorosulfonimide and 0.5% by mass of lithium difluorophosphate to make the concentration of the lithium hexafluorophosphate be 1mol/L, and preparing the lithium ion battery nonaqueous electrolyte.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 9
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises 0.2 mass percent of tetraacetylsilane, 1 mass percent of ethylene sulfate, 0.5 mass percent of vinylene carbonate and 1 mass percent of 1, 3-propane sultone additive based on the total mass of the nonaqueous electrolyte as 100 percent, lithium salt comprises lithium hexafluorophosphate with the concentration of 1mol/L, and lithium difluorophosphate with the mass percent of 0.8 percent, lithium difluorosulfonimide with the mass percent of 0.5 percent and lithium difluorophosphate with the mass percent of 0.5 percent, and the balance is a nonaqueous solvent, wherein the nonaqueous solvent is composed of ethylene carbonate, ethyl methyl carbonate and diethyl carbonate according to the mass ratio of 3:5: 2.
The preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was prepared in a glove box with a nitrogen content of 99.999%, an actual oxygen content of 0.1ppm and a moisture content of 0.1 ppm. Uniformly mixing ethylene carbonate, ethyl methyl carbonate and a diethyl carbonate battery-grade organic solvent in a mass ratio of 3:5:2 by taking the total mass of the nonaqueous electrolyte as 100%, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding 0.2% by mass of tetraethyl alkynyl silane, 1% by mass of ethylene sulfate, 0.5% by mass of vinylene carbonate and 1% by mass of 1, 3-propane sultone, and adding 0.8% by mass of lithium difluorophosphate, 0.5% by mass of lithium bis (fluorosulfonyl) imide and 0.5% by mass of lithium difluorophosphate to make the concentration of the lithium hexafluorophosphate be 1mol/L, thereby preparing the lithium ion battery nonaqueous electrolyte.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 10
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises 1% of tetraacetylsilane, 1% of vinyl sulfate, 0.5% of vinylene carbonate and 1% of 1, 3-propane sultone by mass percentage based on 100% of the total mass of the nonaqueous electrolyte, lithium salt comprises lithium hexafluorophosphate with the concentration of 1mol/L, 0.8% of lithium difluorophosphate, 0.5% of lithium difluorosulfonimide and 0.5% of lithium difluorophosphate by mass percentage, and the balance is a nonaqueous solvent, wherein the nonaqueous solvent is composed of vinyl carbonate, ethyl methyl carbonate and diethyl carbonate in a mass ratio of 3:5: 2.
The preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was prepared in a glove box with a nitrogen content of 99.999%, an actual oxygen content of 0.1ppm and a moisture content of 0.1 ppm. Uniformly mixing ethylene carbonate, ethyl methyl carbonate and a diethyl carbonate battery-grade organic solvent in a mass ratio of 3:5:2 by taking the total mass of the nonaqueous electrolyte as 100%, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding 1% by mass of tetraethyl alkynyl silane, 1% by mass of ethylene sulfate, 0.5% by mass of vinylene carbonate and 1% by mass of 1, 3-propane sultone, and adding 0.8% by mass of lithium difluorophosphate, 0.5% by mass of lithium difluorosulfonimide and 0.5% by mass of lithium difluorophosphate to make the concentration of the lithium hexafluorophosphate be 1mol/L, thereby preparing the lithium ion battery nonaqueous electrolyte.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 11
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises 2.5 mass percent of tetraacetylsilane, 1 mass percent of ethylene sulfate, 0.5 mass percent of vinylene carbonate and 1 mass percent of 1, 3-propane sultone additive, wherein the lithium salt comprises lithium hexafluorophosphate with the concentration of 1mol/L, 0.8 mass percent of lithium difluorophosphate, 0.5 mass percent of lithium difluorosulfonimide and 0.5 mass percent of lithium difluorophosphate, and the balance is a nonaqueous solvent, and the nonaqueous solvent consists of ethylene carbonate, ethyl methyl carbonate and diethyl carbonate in a mass ratio of 3:5:2, based on the total mass of the nonaqueous electrolyte as 100%.
The preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was prepared in a glove box with a nitrogen content of 99.999%, an actual oxygen content of 0.1ppm and a moisture content of 0.1 ppm. Uniformly mixing ethylene carbonate, ethyl methyl carbonate and a diethyl carbonate battery-grade organic solvent in a mass ratio of 3:5:2 by taking the total mass of the nonaqueous electrolyte as 100%, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding 2.5% by mass of tetraacetylsilane, 1% by mass of ethylene sulfate, 0.5% by mass of vinylene carbonate and 1% by mass of 1, 3-propane sultone respectively, adding 0.8% by mass of lithium difluorophosphate, 0.5% by mass of lithium difluorosulfonimide and 0.5% by mass of lithium difluorophosphate respectively, and enabling the concentration of the lithium hexafluorophosphate to be 1mol/L to prepare the lithium ion battery nonaqueous electrolyte.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 12
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises additives of 0.05% by mass of tetravinylsiloxane, 0.05% by mass of tetraacetylsilane, 1% by mass of vinyl sulfate, 0.5% by mass of vinylene carbonate and 1% by mass of 1, 3-propane sultone, wherein lithium salt comprises lithium hexafluorophosphate with the concentration of 1mol/L, 0.8% by mass of lithium difluorophosphate, 0.5% by mass of lithium difluorosulfonimide and 0.5% by mass of lithium difluorophosphate, and the balance of nonaqueous solvent, wherein the nonaqueous electrolyte is composed of vinyl carbonate, ethyl methyl carbonate aqueous solvent and diethyl carbonate according to the mass ratio of 3:5: 2.
The preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was prepared in a glove box with a nitrogen content of 99.999%, an actual oxygen content of 0.1ppm and a moisture content of 0.1 ppm. Uniformly mixing ethylene carbonate, ethyl methyl carbonate and a diethyl carbonate battery-grade organic solvent in a mass ratio of 3:5:2 by taking the total mass of the nonaqueous electrolyte as 100%, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding 0.05% of tetraenylsiloxane, 0.05% of tetraacetylsilane, 1% of ethylene sulfate, 0.5% of vinylene carbonate and 1% of 1, 3-propane sultone in percentage by mass, adding 0.8% of lithium difluorophosphate, 0.5% of lithium difluorosulfonimide and 0.5% of lithium difluorophosphate in percentage by mass to make the concentration of the lithium hexafluorophosphate be 1mol/L, and preparing the lithium ion battery nonaqueous electrolyte.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 13
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises 0.2 mass percent of tetraenylsiloxane, 0.2 mass percent of tetraacetylsilane, 1 mass percent of vinyl sulfate, 0.5 mass percent of vinylene carbonate and 1 mass percent of 1, 3-propane sultone as additives based on the total mass of the nonaqueous electrolyte as 100 percent, lithium salts comprise lithium hexafluorophosphate with the concentration of 1mol/L, 0.8 mass percent of lithium difluorophosphate, 0.5 mass percent of lithium difluorosulfonimide and 0.5 mass percent of lithium difluorophosphate, and the balance is a nonaqueous solvent, wherein the nonaqueous electrolyte consists of vinyl carbonate, methyl ethyl carbonate aqueous solvent and diethyl carbonate in a mass ratio of 3:5: 2.
The preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was prepared in a glove box with a nitrogen content of 99.999%, an actual oxygen content of 0.1ppm and a moisture content of 0.1 ppm. Uniformly mixing ethylene carbonate, ethyl methyl carbonate and a diethyl carbonate battery-grade organic solvent in a mass ratio of 3:5:2 by taking the total mass of the nonaqueous electrolyte as 100%, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding 0.2% of tetraenylsiloxane, 0.2% of tetraacetylsilane, 1% of ethylene sulfate, 0.5% of vinylene carbonate and 1% of 1, 3-propane sultone in percentage by mass, adding 0.8% of lithium difluorophosphate, 0.5% of lithium difluorosulfonimide and 0.5% of lithium difluorophosphate in percentage by mass to make the concentration of the lithium hexafluorophosphate be 1mol/L, and preparing the lithium ion battery nonaqueous electrolyte.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 14
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises 1% by mass of tetraenylsiloxane, 1% by mass of tetraacetylsilane, 1% by mass of vinyl sulfate, 0.5% by mass of vinylene carbonate and 1% by mass of 1, 3-propane sultone as additives based on the total mass of the nonaqueous electrolyte as 100%, wherein lithium salts comprise lithium hexafluorophosphate with the concentration of 1mol/L, 0.8% by mass of lithium difluorophosphate, 0.5% by mass of lithium difluorosulfonimide and 0.5% by mass of lithium difluorophosphate, and the balance is a nonaqueous solvent, and the nonaqueous solvent is composed of vinyl carbonate, ethyl methyl carbonate and diethyl carbonate in a mass ratio of 3:5: 2.
The preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was prepared in a glove box with a nitrogen content of 99.999%, an actual oxygen content of 0.1ppm and a moisture content of 0.1 ppm. Uniformly mixing ethylene carbonate, ethyl methyl carbonate and a diethyl carbonate battery-grade organic solvent in a mass ratio of 3:5:2 by taking the total mass of the nonaqueous electrolyte as 100%, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding 1% by mass of tetraenylsiloxane, 1% by mass of tetraacetylsilane, 1% by mass of ethylene sulfate, 0.5% by mass of vinylene carbonate and 1% by mass of 1, 3-propane sultone, respectively, adding 0.8% by mass of lithium difluorophosphate, 0.5% by mass of lithium difluorosulfonimide and 0.5% by mass of lithium difluorophosphate, respectively, so that the concentration of the lithium hexafluorophosphate is 1mol/L, and preparing the lithium ion battery nonaqueous electrolyte.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 15
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises 2.5 mass percent of tetraenylsiloxane, 2.5 mass percent of tetraacetylsilane, 1 mass percent of vinyl sulfate, 0.5 mass percent of vinylene carbonate and 1 mass percent of 1, 3-propane sultone as additives based on the total mass of the nonaqueous electrolyte as 100 percent, lithium salts comprise lithium hexafluorophosphate with the concentration of 1mol/L, 0.8 mass percent of lithium difluorophosphate, 0.5 mass percent of lithium difluorosulfonimide and 0.5 mass percent of lithium difluorophosphate, and the balance is a nonaqueous solvent, wherein the nonaqueous electrolyte consists of vinyl carbonate, methyl ethyl carbonate aqueous solvent and diethyl carbonate in a mass ratio of 3:5: 2.
The preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was prepared in a glove box with a nitrogen content of 99.999%, an actual oxygen content of 0.1ppm and a moisture content of 0.1 ppm. Uniformly mixing ethylene carbonate, ethyl methyl carbonate and a diethyl carbonate battery grade organic solvent in a mass ratio of 3:5:2 by taking the total mass of the nonaqueous electrolyte as 100%, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding 2.5% by mass of tetraenylsiloxane, 2.5% by mass of tetraacetylsilane, 1% by mass of ethylene sulfate, 0.5% by mass of vinylene carbonate and 1% by mass of 1, 3-propane sultone respectively, adding 0.8% by mass of lithium difluorophosphate, 0.5% by mass of lithium difluorosulfonimide and 0.5% by mass of lithium difluorophosphate respectively, and preparing the lithium hexafluorophosphate into the lithium ion battery nonaqueous electrolyte, wherein the concentration of the lithium hexafluorophosphate is 1 mol/L.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Comparative example 1
The comparative example is different from example 4 in that the amount of the tetravinylsiloxane was 25% by mass based on 100% by mass of the total nonaqueous electrolytic solution, the amount of the nonaqueous solvent was adjusted to 100% by mass of the total electrolytic solution, and the other raw materials, the compounding ratios, and the mass percentages of the respective components were the same as those in example 4.
Comparative example 2
The comparative example is different from example 8 in that the content of the tetraacetylsilane additive by mass is 25% based on 100% of the total mass of the nonaqueous electrolytic solution, the amount of the nonaqueous solvent is adjusted adaptively so that the total amount of the electrolytic solution is 100%, and the other raw materials, the compounding ratio and the content by mass of each component are the same as those of example 8.
Comparative example 3
The difference between the comparative example and the example 12 is that no tetraenylsiloxane and tetraenylsilane additives are added, the amount of the non-aqueous solvent is adaptively adjusted to make the total amount of the electrolyte be 100%, and the mass percentage of other raw materials, the proportion and the components are the same as those in the example 12.
Comparative example 4
The comparative example is different from example 12 in that the amount of the non-aqueous electrolyte is adjusted to 100% by mass based on 100% by mass of the total non-aqueous electrolyte, the amount of the tetravinylsiloxane additive is 20% by mass, the amount of the tetrakisvinylsilane additive is 20% by mass, the amount of the non-aqueous solvent is adjusted to 100% by mass of the total electrolyte, and the other raw materials, the mixture ratio and the mass percentage of each component are the same as those of example 12.
Test conditions
The lithium ion batteries prepared in examples 1 to 15 and comparative examples 1 to 4 were respectively subjected to a high-temperature storage performance test, the test method was as follows:
charging the lithium ion battery to 4.2V at a constant current of 1C at 25 ℃, then charging the lithium ion battery to a constant voltage of 0.05C, testing the thickness of the lithium ion battery before storage and recording the thickness as D0. Then the fully charged battery is placed in a 60 ℃ oven for storage for 30 days, and the thickness after storage is tested and recorded as D1The thickness expansion rate with respect to the lithium ion battery before storage is calculated according to the following formula:
thickness expansion ratio (%) - (D)1-D0)/D0×100％。
Charging the lithium ion battery to 4.2V at a constant current of 1C at 25 ℃, then charging to a constant voltage of 4.2V until the current is less than 0.05C, and then discharging to 3.0V at a constant current of 0.5C, testing the discharge capacity of the lithium ion battery at the moment and recording as R0(ii) a Charging to 4.2V at a constant current of 1C, then charging to a current of less than 0.05C at a constant voltage of 4.2V, then storing the lithium ion battery at 60 ℃ for 30 days, and after the storage is finished, discharging to 3.0V at a constant current of 1C; charging to 4.2V at constant current of 1C, charging to current less than 0.05C at constant voltage of 4.2V, discharging to 3.0V at constant current of 0.5C, testing discharge capacity of the lithium ion battery at the moment, and recording as R1. The capacity retention rate relative to the lithium ion battery before storage was calculated according to the following formula:
capacity conservationPercent (%) is (R)1/R0)×100％
The results of the test are shown in table 1:
table 1:
as can be seen from the data in table 1, the additive-containing nonaqueous electrolyte solution is used in the present invention, and the lithium ion batteries prepared in the above examples 1 to 15 are tested for high-temperature storage performance, and when the mass content of the first compound additive in the nonaqueous electrolyte solution is 0.2%, the lithium ion batteries show the best overall performance, wherein the capacity retention rate of the lithium ion batteries provided in examples 5, 9 and 13 is as high as 94.6% or more, further indicating that the lithium ion batteries prepared by using the electrolyte solution of the present invention have the advantages of high storage capacity retention rate and long cycle life; compared with comparative examples 1 to 4, the gas production volume growth rates of the lithium ion batteries provided in examples 5, 9 and 13 at a high temperature of 60 ℃ are all below 6.5%, which indicates that the thickness growth of the lithium ion batteries in examples 5, 9 and 13 is much smaller than that of the lithium ion batteries in comparative examples 1 to 4, and further shows that the volume expansion of the batteries can be relieved by using the electrolyte provided by the invention, so that the electrolyte provided by the invention is applied to the lithium ion batteries and has excellent high-temperature storage stability.
Compared with examples 4-7, the best mass percentage content exists when the tetravinyl siloxane additive is added, and when the total mass of the non-aqueous electrolyte is 100%, and the mass percentage content of the tetravinyl siloxane additive is 0.2%, the electrolyte provided by the invention can form a relatively uniform and compact CEI film on the surface of the cathode material in the storage process, so that the prepared lithium ion battery has excellent high-temperature storage stability.
Similarly, compared with examples 8-11, the best mass percentage content exists when the tetraethyl orthosilicate additive is added, and when the mass percentage content of the added tetraethyl orthosilicate additive is 0.2% based on 100% of the total mass of the nonaqueous electrolyte, the electrolyte provided by the invention can form a uniform and compact SEI film on the surface of a negative electrode material in the storage process, so that the prepared lithium ion battery has excellent high-temperature storage stability.
In summary, by comparing examples 12 to 15, when the tetraenylsiloxane formed on the positive electrode and the tetraenylsilane formed on the negative electrode are simultaneously added, the high temperature storage performance of the lithium ion battery can be more excellent.
Comparative examples 1, 2 and 4 show that adding a much higher amount of tetravinylsiloxane or tetrakisvinylsilane results in a thicker SEI film, increased impedance of the battery, and unfavorable improvement of electrochemical performance of the lithium ion battery; comparative example 3 shows that stable SEI films cannot be formed on the surfaces of the positive electrode and the negative electrode of a lithium ion battery without adding tetraenylsiloxane and tetraenylsilane, and thus poor high-temperature storage performance is exhibited.
The applicant states that the present invention is illustrated by the above examples of the process of the present invention, but the present invention is not limited to the above process steps, i.e. it is not meant that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (10)
1. A lithium ion battery non-aqueous electrolyte solution is characterized by comprising an electrolyte, a non-aqueous solvent and an additive, wherein the additive comprises a first compound with a structure shown in a formula 1 and a cyclic ester additive:
wherein R is1、R2、R3And R4Independently selected from-O-CH ═ CH2Or an ethynyl group.
2. The nonaqueous electrolyte solution for lithium ion batteries according to claim 1, wherein the first compound comprises a second compound having a structure represented by formula 2 or a third compound having a structure represented by formula 3:
preferably, the mass percentage of the first compound in the lithium ion battery nonaqueous electrolyte is 0.05% to 5%.
3. The nonaqueous electrolyte solution for lithium ion batteries according to claim 1 or 2, wherein the content of the cyclic ester additive in the nonaqueous electrolyte solution for lithium ion batteries is 0.05 to 20% by mass.
4. The nonaqueous electrolyte solution for a lithium ion battery according to any one of claims 1 to 3, wherein the cyclic ester additive in the nonaqueous electrolyte solution for a lithium ion battery includes any one of a cyclic carbonate additive, a cyclic sultone additive, or a cyclic sulfate additive, or a combination of at least two thereof.
5. The nonaqueous electrolyte solution for lithium ion batteries according to claim 4, wherein the cyclic carbonate additive comprises any one of vinylene carbonate, fluoroethylene carbonate or ethylene carbonate or a combination of at least two of them;
preferably, the cyclic sultone additive comprises any one or two of 1, 3-propane sultone and 1, 3-propylene sultone.
6. The nonaqueous electrolyte solution for lithium ion batteries according to claim 4 or 5, wherein the cyclic sulfate-based additive comprises any one of vinyl sulfate, propylene sulfate, or a combination of at least two thereof.
7. The nonaqueous electrolyte solution for a lithium ion battery according to any one of claims 1 to 6, wherein the electrolyte is a lithium salt;
preferably, the lithium salt comprises lithium hexafluorophosphate;
preferably, the concentration of lithium hexafluorophosphate in the lithium ion battery nonaqueous electrolyte is 0.5mol/L to 2 mol/L;
preferably, the additive further comprises a lithium salt additive;
preferably, the lithium salt additive comprises any one of or a combination of at least two of lithium bis (oxalate) difluorophosphate, lithium difluorooxalate borate, lithium bis (fluorosulfonyl) imide or lithium bis (trifluoromethylsulfonyl) imide;
preferably, the lithium salt additive is contained in the lithium ion battery nonaqueous electrolyte in an amount of 0.05 to 20 mass%.
8. The nonaqueous electrolyte solution for a lithium ion battery according to any one of claims 1 to 7, wherein the nonaqueous solvent comprises any one of ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene carbonate, or diethyl carbonate, or a combination of at least two of them;
preferably, the mass percentage of the nonaqueous solvent in the nonaqueous electrolyte of the lithium ion battery is 60-85%.
9. A lithium ion battery, characterized in that the lithium ion battery comprises the lithium ion battery nonaqueous electrolytic solution according to any one of claims 1 to 8.
10. The lithium ion battery of claim 9, further comprising a positive electrode current collector and a positive electrode active material coated on the positive electrode current collector, a negative electrode current collector and a negative electrode active material coated on the negative electrode current collector, and a separator;
preferably, the positive active material includes any one or a combination of at least two of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt manganese oxide, or lithium nickel cobalt aluminum oxide;
preferably, the negative active material includes any one of soft carbon, hard carbon, artificial graphite, natural graphite, silicon oxy compound, silicon carbon compound, or lithium titanate, or a combination of at least two thereof.
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| CN114709481A (en) * | 2022-04-02 | 2022-07-05 | 远景动力技术(江苏)有限公司 | Non-aqueous electrolyte and lithium ion battery thereof |
| CN114709480A (en) * | 2022-04-02 | 2022-07-05 | 远景动力技术(江苏)有限公司 | Non-aqueous electrolyte and lithium ion battery thereof |
| CN114899484A (en) * | 2022-04-02 | 2022-08-12 | 远景动力技术(江苏)有限公司 | Non-aqueous electrolyte and lithium ion battery thereof |
| CN114709480B (en) * | 2022-04-02 | 2023-09-26 | 远景动力技术(河北)有限公司 | Nonaqueous electrolyte and lithium ion battery thereof |
| CN114899484B (en) * | 2022-04-02 | 2023-10-27 | 远景动力技术(江苏)有限公司 | Nonaqueous electrolyte and lithium ion battery thereof |
| CN114709481B (en) * | 2022-04-02 | 2023-10-31 | 远景动力技术(江苏)有限公司 | Nonaqueous electrolyte and lithium ion battery thereof |
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