CN113991178B - Nonaqueous electrolyte for lithium ion battery and application thereof - Google Patents
Nonaqueous electrolyte for lithium ion battery and application thereof Download PDFInfo
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- CN113991178B CN113991178B CN202111250465.9A CN202111250465A CN113991178B CN 113991178 B CN113991178 B CN 113991178B CN 202111250465 A CN202111250465 A CN 202111250465A CN 113991178 B CN113991178 B CN 113991178B
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/0568—Liquid materials characterised by the solutes
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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
- H01M10/0569—Liquid materials characterised by the solvents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a non-aqueous electrolyte of a lithium ion battery and application thereof. The lithium ion battery nonaqueous electrolyte comprises an electrolyte, a nonaqueous solvent and an additive, wherein the additive comprises a first compound and a cyclic ester additive. The lithium ion battery nonaqueous 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 anode material and the cathode material, and meanwhile, the high-temperature storage performance of the lithium ion battery is improved and the gas production is inhibited.
Description
Technical Field
The invention belongs to the field of batteries, and particularly relates to a nonaqueous electrolyte for a lithium ion battery and application of the nonaqueous electrolyte.
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 the main energy storage devices of the current portable electronic equipment, and simultaneously shows good performance in the application fields of electric automobiles, intelligent Internet of things and the like.
In order to further meet the ever-evolving needs of applications, lithium ion batteries are also required to have higher energy densities. At present, the energy density of the lithium ion battery is improved in two main ways in the prior art: one way is to use a positive electrode material with high content of nickel element to increase specific capacity; another way is to raise 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 positive electrode material is reduced due to the excessively high content of nickel element, and the electrolyte is subjected to oxidative decomposition side reaction due to unstable trivalent nickel ions; on the other hand, merely raising the charge cutoff voltage of the battery raises the reaction potential of the positive electrode material, and causes a series of problems such as swelling of the battery and an increase in interface impedance, accompanied by an oxidative decomposition process of the electrolyte. In summary, the foregoing demonstrates that more stringent requirements are placed on electrolyte materials.
In view of the above, there is a need in the art to develop and provide a solid electrolyte interphase (Solid Electrolyte Interface, SEI) that can solve the above problems and is stable, which can not only suppress side reactions of the electrolyte with the positive and negative electrodes, but also improve the high-temperature storage performance and safety performance of the lithium ion secondary battery.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a non-aqueous electrolyte for a lithium ion battery and application thereof. The lithium ion battery nonaqueous 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 anode material and the cathode material, and meanwhile, the high-temperature storage performance of the lithium ion battery is improved and the gas production is inhibited.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a lithium ion battery nonaqueous electrolyte comprising an electrolyte, a nonaqueous solvent, and an additive comprising a first compound having a structure represented by formula 1 and a cyclic ester additive:
wherein R is 1 、R 2 、R 3 And R is 4 Independently selected from-O-ch=ch 2 Or ethynyl.
On one hand, the first compound in the additive provided by the invention has higher electron cloud density of double bonds due to stronger electron pushing effect of oxygen atoms, so that oxidation polymerization reaction can be more easily generated at the positive electrode under voltage regulation and control, and a multidimensional network structure with good flexibility is formed; on the other hand, the carbon atoms in the ethynyl are sp hybridized, and after the proportion of the s orbit component to the hybridized orbit is increased, the electron withdrawing property of the alkynyl is stronger, so that the reduction polymerization reaction is easy to occur at the negative electrode, and a multidimensional network with certain rigidity is formed. In conclusion, the compound use of the first compound and the cyclic ester additive in the electrolyte provided by the invention can effectively promote the formation of a compact SEI film at the positive electrode interface and the negative electrode interface, thereby improving the high-temperature storage performance of the battery.
Preferably, the first compound includes 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 nonaqueous electrolyte solution of the lithium ion battery is 0.05% to 5%, for example, may be 0.05%,0.1%,0.5%,1%,2% or 5%, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the mass percentage of the cyclic ester additive in the nonaqueous electrolyte of the lithium ion battery is 0.05% to 20%, for example, may be 0.05%,0.5%,1%,5%,10% or 20%, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the cyclic ester additive in the nonaqueous electrolyte of the lithium ion battery includes any one or a combination of at least two of a cyclic carbonate additive, a cyclic sulfonate additive, or a cyclic sulfate additive, and for example, the cyclic carbonate additive, the cyclic sulfonate additive, and the cyclic sulfonate additive may be any one of a cyclic carbonate additive, a cyclic sulfonate additive, a cyclic carbonate additive, a cyclic sulfate additive, a cyclic sulfonate additive, and a cyclic sulfate, but not limited to the listed types, and other types not listed in the scope of the cyclic ester additive are equally applicable.
Preferably, the cyclic carbonate additive comprises any one or a combination of at least two of vinylene carbonate, fluoroethylene carbonate or ethylene carbonate, for example, vinylene carbonate, fluoroethylene carbonate and ethylene carbonate, fluoroethylene carbonate and vinylene carbonate or ethylene carbonate, but not limited to the listed types, other non-listed types within the scope of the cyclic carbonate additive are equally applicable.
Preferably, the cyclic sultone additive includes any one or a combination of two of 1, 3-propane sultone and 1, 3-propene sultone, and may be, for example, 1, 3-propane sultone and 1, 3-propene sultone, 1, 3-propane sultone or 1, 3-propene sultone.
Preferably, the cyclic sulfate additive includes any one or a combination of at least two of vinyl sulfate and propylene sulfate, and for example, the cyclic sulfate additive may be vinyl sulfate and propylene sulfate, vinyl sulfate or propylene sulfate.
Preferably, the electrolyte is a lithium salt.
Preferably, the lithium salt comprises lithium hexafluorophosphate.
The concentration of lithium hexafluorophosphate in the nonaqueous electrolyte of the lithium ion battery is preferably 0.5mol/L to 2mol/L, for example, may be 0.5mol/L,1mol/L,1.5mol/L or 2mol/L, but is not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
Preferably, the additive further comprises a lithium salt additive.
Preferably, the lithium salt additive comprises any one or a combination of at least two of lithium difluorophosphate, lithium difluorooxalato borate, lithium difluorosulfonimide or lithium bistrifluoromethylsulfonylimide, for example, lithium difluorophosphate and lithium difluorophosphate, lithium difluorooxalato borate or lithium difluorosulfonimide, but not limited to the listed types, and other non-listed types are equally applicable within the scope of the lithium salt additive.
Preferably, the mass percentage of the lithium salt additive in the nonaqueous electrolyte of the lithium ion battery is 0.05% to 20%, for example, may be 0.05%,0.5%,1%,5%,10% or 20%, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the nonaqueous solvent includes any one or a combination of at least two of ethylene carbonate, dimethyl carbonate, ethylmethyl carbonate, propylene carbonate or diethyl carbonate, for example, ethylene carbonate and dimethyl carbonate, ethylmethyl carbonate and propylene carbonate or diethyl carbonate, but not limited to the listed types, and other non-listed types are equally applicable in the nonaqueous solvent range.
Preferably, the mass percentage of the nonaqueous solvent in the nonaqueous electrolyte of the lithium ion battery is 60% to 85%, for example, 60%,65%,70%,75%,80% or 85%, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
In a second aspect, the present invention provides a lithium ion battery comprising the lithium ion battery nonaqueous electrolyte of the first aspect.
Preferably, 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.
Preferably, the positive electrode 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 for example, may be 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 not limited to the listed types, and other non-listed types are equally applicable within the scope of the positive electrode active material.
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 oxy-carbon compound, silicon carbon compound, or lithium titanate, and for example, soft carbon and hard carbon, artificial graphite and natural graphite, silicon oxy-carbon compound, silicon carbon compound, or lithium titanate may be used, but not limited to the listed types, and other non-listed types within the scope of the negative electrode active material are equally applicable.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a lithium ion battery nonaqueous electrolyte capable of inhibiting the reaction between an electrolyte and a positive electrode/negative electrode in a high-temperature state, thereby improving the high-temperature storage performance of a lithium ion battery. The electron cloud density of the substituent is enhanced by adopting the second compound additive, so that the electron cloud density of the substituent is beneficial to oxidation polymerization reaction, and chain growth reaction and compact and uniform SEI film formation on the surface of the positive electrode material are caused; the third compound is favorable for carrying out reduction polymerization reaction due to electron-deficient characteristic of the ethynyl group, so that an SEI film is formed on the surface of the anode material; under the synergistic effect of the two, 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 scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The prior art scheme improves the energy density of the lithium ion battery by adopting a positive electrode material with high content of nickel element and improving the charge cut-off voltage. However, the solutions disclosed in the prior art all have adverse effects on the electrolyte, for example, resulting in side reactions, gas production, and increased interfacial resistance.
In order to solve the technical problems, the invention provides a non-aqueous electrolyte of a lithium ion battery and application thereof.
The embodiment of the invention provides a lithium ion battery nonaqueous electrolyte, which comprises an electrolyte, a nonaqueous 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 is 1 、R 2 、R 3 And R is 4 Independently selected from-O-CH＝CH 2 Or ethynyl.
The first compound additive employed in the present invention may be enhanced (selected from-O-ch=ch 2 Substituent) or weakens (selects acetylene substituent) the electron cloud density of the substituent, is favorable for oxidation or reduction polymerization reaction, thereby generating chain growth reaction and forming compact and uniform SEI film on the surface of the electrode material, and meanwhile, the SEI film is compounded with a cyclic ester additive for use, so that the high-temperature storage performance of the battery is optimized.
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 cyclic ester additive is present in the lithium ion battery nonaqueous electrolyte in an amount of 0.05% to 20% by mass.
In some embodiments, the cyclic ester additive in the lithium ion battery nonaqueous electrolyte comprises any one or a combination of at least two of a cyclic carbonate additive, a cyclic sulfonate additive, or a cyclic sulfate additive.
In some embodiments, the cyclic carbonate additive includes any one or a combination of at least two of vinylene carbonate, fluoroethylene carbonate, or ethylene carbonate.
In some embodiments, the cyclic sultone-based additive comprises any one or a combination of two of 1, 3-propane sultone, 1, 3-propenoic acid lactone.
In some embodiments, the cyclic sulfate additive includes any one or a combination of at least two of vinyl sulfate, propylene sulfate.
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 non-aqueous electrolyte is 0.5mol/L to 2mol/L.
In some embodiments, the additive further comprises a lithium salt additive.
In some embodiments, the lithium salt additive comprises any one or a combination of at least two of lithium difluorophosphate, lithium difluorooxalato borate, lithium difluorosulfonimide, or lithium bistrifluoromethylsulfonimide.
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 nonaqueous solvent comprises any one or a combination of at least two of ethylene carbonate, dimethyl carbonate, ethylmethyl carbonate, propylene carbonate, or diethyl carbonate.
In some embodiments, the non-aqueous solvent in the non-aqueous electrolyte of the lithium ion battery is 60% to 85% by mass.
In one embodiment, a lithium ion battery is provided that includes the lithium ion battery nonaqueous electrolyte.
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 an embodiment, the positive electrode 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.
In an embodiment, 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, a silicon oxygen compound, a silicon carbon compound, or lithium titanate.
Example 1
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises, based on 100% of the total mass of the nonaqueous electrolyte, 2.5% of tetravinyl siloxane, 2.5% of vinylene carbonate, 2.5% of 1, 3-propane sultone and 5% of an additive of vinyl sulfate, wherein the lithium salt comprises 1mol/L lithium hexafluorophosphate, 2.5% of lithium difluorosulfimide and 5% of lithium difluorophosphate, and the balance of a nonaqueous solvent, wherein the nonaqueous solvent consists of vinyl carbonate, methyl ethyl carbonate and diethyl carbonate in a mass ratio of 3:5:2.
The preparation method of the nonaqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was formulated in a glove box where the nitrogen content was 99.999%, the actual oxygen content in the glove box was 0.1ppm, and the moisture content was 0.1ppm. And (3) uniformly mixing the ethylene carbonate, the methyl ethyl carbonate and the 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% of tetravinyl siloxane, 2.5% of ethylene carbonate, 2.5% of 1, 3-propane sultone and 5% of ethylene sulfate by mass percent, and adding 2.5% of lithium difluorophosphate, 2.5% of lithium difluorosulfimide and 5% of lithium difluorophosphate by mass percent to ensure that the concentration of the lithium hexafluorophosphate is 1mol/L, thereby preparing the nonaqueous electrolyte of the lithium ion battery.
The preparation method of the lithium ion battery comprises the following steps:
the positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O 2 Fully stirring and uniformly mixing the conductive agent acetylene black and the binder polyvinylidene fluoride in an N-methyl pyrrolidone solvent system according to the mass ratio of 95:3:2, coating the mixture on an aluminum foil, drying and cold pressing the aluminum foil to obtain a positive electrode plate, wherein the compacted density of the positive electrode plate is 3.5g/cm 3 。
Graphite as negative electrode active material, acetylene black as conductive agent and butadiene as adhesiveFully stirring and uniformly mixing benzene rubber and thickener sodium carboxymethyl cellulose in a deionized water solvent system according to a mass ratio of 96:2:1:1, coating the mixture on a copper foil, drying, and cold pressing to obtain a negative electrode plate, wherein the compaction density of the negative electrode plate is 1.65g/cm 3 。
The separator was obtained by using polyethylene having a thickness of 9 μm as a base film and coating a nano alumina coating having a thickness of 3 μm on the base film.
And sequentially stacking the positive pole piece, the diaphragm and the negative pole piece, so that the diaphragm is positioned between the positive pole piece and the negative pole piece to play a role in isolation, and stacking to obtain the bare cell.
And (3) 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-dividing and the like to obtain the finished product of the flexible package lithium ion secondary battery.
Example 2
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises 0.05% of tetravinyl siloxane, 0.025% of vinylene carbonate and 0.025% of 1, 3-propane sultone additive by mass percent based on 100% of the total mass of the nonaqueous electrolyte, wherein lithium salt comprises 0.5mol/L of lithium hexafluorophosphate, 5% of lithium difluorosulfimide and 10% of lithium difluorophosphate by mass percent, and the balance of nonaqueous solvent is composed of ethylene carbonate, methyl ethyl carbonate and diethyl carbonate according to a mass ratio of 3:5:2.
The preparation method of the nonaqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was formulated in a glove box where the nitrogen content was 99.999%, the actual oxygen content in the glove box was 0.1ppm, and the moisture content was 0.1ppm. And (3) uniformly mixing the ethylene carbonate, the methyl ethyl carbonate and the 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 the lithium hexafluorophosphate which is fully dried into the nonaqueous solvent, adding 0.05% of tetravinyl siloxane, 0.025% of vinylene carbonate and 0.025% of 1, 3-propane sultone in percentage by mass, and adding 5% of lithium difluorophosphate, 5% of lithium difluorosulfimide and 10% of lithium difluorooxalate in percentage by mass to obtain the lithium hexafluorophosphate with the concentration of 0.5mol/L, thereby preparing the nonaqueous electrolyte of the lithium ion battery.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of this example is the same as that of example 1.
Example 3
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises, based on 100% of the total mass of the nonaqueous electrolyte, 5% of tetravinyl siloxane, 5% of vinylene carbonate, 10% of 1, 3-propane sultone and 5% of an additive of vinyl sulfate, wherein lithium salt comprises lithium hexafluorophosphate with a concentration of 2mol/L and lithium difluorophosphate with a mass percentage of 0.025% and lithium difluorosulfimide with a mass percentage of 0.025%, respectively, and the balance of a nonaqueous solvent is composed of ethylene carbonate, methyl ethyl carbonate and diethyl carbonate according to a mass ratio of 3:5:2.
The preparation method of the nonaqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was formulated in a glove box where the nitrogen content was 99.999%, the actual oxygen content in the glove box was 0.1ppm, and the moisture content was 0.1ppm. And (2) uniformly mixing the ethylene carbonate, the methyl ethyl carbonate and the diethyl carbonate battery grade organic solvent in a mass ratio of 3:5:2 based on 100% of the total mass of the nonaqueous electrolyte, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding tetravinyl siloxane, vinylene carbonate, 1, 3-propane sultone and vinyl sulfate in a mass percentage of 5% respectively, and adding lithium difluorophosphate and lithium difluorosulfimide in a mass percentage of 0.025% respectively to ensure that the concentration of lithium hexafluorophosphate is 2mol/L to prepare the nonaqueous electrolyte of the lithium ion battery.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of this 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 tetravinyl siloxane, 1% of vinyl sulfate, 0.5% of vinylene carbonate and 1% of 1, 3-propane sultone additive by mass percent based on 100% of the total mass of the nonaqueous electrolyte, wherein lithium salt comprises 1mol/L lithium hexafluorophosphate, 0.5% of lithium difluorosulfimide and 0.5% of lithium difluorophosphate by mass percent, and the balance of nonaqueous solvent is composed of 3:5:2 of ethylene carbonate, methyl ethyl carbonate and diethyl carbonate by mass percent.
The preparation method of the nonaqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was formulated in a glove box where the nitrogen content was 99.999%, the actual oxygen content in the glove box was 0.1ppm, and the moisture content was 0.1ppm. And (3) uniformly mixing the ethylene carbonate, the methyl ethyl carbonate and the 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 tetravinyl siloxane, 1% of vinyl sulfate, 0.5% of ethylene carbonate and 1% of 1, 3-propane sultone by mass percent, and adding 0.8% of lithium difluorophosphate, 0.5% of lithium difluorosulfimide and 0.5% of lithium difluorophosphate by mass percent to prepare 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 this example is the same as that of example 1.
Example 5
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises 0.2% of tetravinyl siloxane, 1% of vinyl sulfate, 0.5% of vinylene carbonate and 1% of 1, 3-propane sultone additive by mass percent based on 100% of the total mass of the nonaqueous electrolyte, wherein lithium salt comprises 1mol/L lithium hexafluorophosphate, 0.5% of lithium difluorosulfimide and 0.5% of lithium difluorophosphate by mass percent, and the balance of nonaqueous solvent is composed of 3:5:2 of ethylene carbonate, methyl ethyl carbonate and diethyl carbonate by mass percent.
The preparation method of the nonaqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was formulated in a glove box where the nitrogen content was 99.999%, the actual oxygen content in the glove box was 0.1ppm, and the moisture content was 0.1ppm. And (3) uniformly mixing the ethylene carbonate, the methyl ethyl carbonate and the 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 tetravinyl siloxane, 1% of vinyl sulfate, 0.5% of ethylene carbonate and 1% of 1, 3-propane sultone by mass percent, and adding 0.8% of lithium difluorophosphate, 0.5% of lithium difluorosulfimide and 0.5% of lithium difluorophosphate by mass percent to prepare 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 this example is the same as that of example 1.
Example 6
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises, based on 100% of the total mass of the nonaqueous electrolyte, 1% of tetravinyl siloxane, 1% of vinyl sulfate, 0.5% of vinylene carbonate and 1% of an additive of 1, 3-propane sultone, wherein the lithium salt comprises 1mol/L lithium hexafluorophosphate, 0.8% of lithium difluorophosphate, 0.5% of lithium difluorosulfimide and 0.5% of lithium difluorophosphate, and the balance of a nonaqueous solvent, and the nonaqueous solvent consists of vinyl carbonate, methyl ethyl carbonate and diethyl carbonate in a mass ratio of 3:5:2.
The preparation method of the nonaqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was formulated in a glove box where the nitrogen content was 99.999%, the actual oxygen content in the glove box was 0.1ppm, and the moisture content was 0.1ppm. And (3) uniformly mixing the ethylene carbonate, the ethylmethyl carbonate and the 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 tetravinyl siloxane, vinyl sulfate, ethylene carbonate and 1, 3-propane sultone in mass percent of 1% respectively, and adding lithium difluorophosphate, lithium difluorosulfimide and lithium difluorophosphate in mass percent of 0.8% and lithium difluorosulfonate of 0.5% respectively to prepare 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 this example is the same as that of example 1.
Example 7
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises, based on 100% of the total mass of the nonaqueous electrolyte, 2.5% of tetravinyl siloxane, 1% of vinyl sulfate, 0.5% of vinylene carbonate and 1% of an additive of 1, 3-propane sultone, wherein the lithium salt comprises 1mol/L lithium hexafluorophosphate, 0.8% of lithium difluorophosphate, 0.5% of lithium difluorosulfimide and 0.5% of lithium difluorophosphate, and the balance of a nonaqueous solvent, and the nonaqueous solvent consists of vinyl carbonate, methyl ethyl carbonate and diethyl carbonate in a mass ratio of 3:5:2.
The preparation method of the nonaqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was formulated in a glove box where the nitrogen content was 99.999%, the actual oxygen content in the glove box was 0.1ppm, and the moisture content was 0.1ppm. And (3) uniformly mixing the ethylene carbonate, the methyl ethyl carbonate and the 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% of tetravinyl siloxane, 1% of vinyl sulfate, 0.5% of ethylene carbonate and 1% of 1, 3-propane sultone by mass percent, and adding 0.8% of lithium difluorophosphate, 0.5% of lithium difluorosulfimide and 0.5% of lithium difluorophosphate by mass percent to prepare 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 this 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 tetraethynyl silane, 1% of vinyl sulfate, 0.5% of vinylene carbonate and 1% of 1, 3-propane sultone additive by mass percent based on 100% of the total mass of the nonaqueous electrolyte, wherein lithium salt comprises 1mol/L lithium hexafluorophosphate, 0.5% of lithium difluorosulfimide and 0.5% of lithium difluorophosphate by mass percent, and the balance of a nonaqueous solvent is composed of ethylene carbonate, ethylmethyl carbonate and diethyl carbonate according to a mass ratio of 3:5:2.
The preparation method of the nonaqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was formulated in a glove box where the nitrogen content was 99.999%, the actual oxygen content in the glove box was 0.1ppm, and the moisture content was 0.1ppm. And (3) uniformly mixing the ethylene carbonate, the ethylmethyl carbonate and the 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 tetraethynyl silane, 1% of ethylene sulfate, 0.5% of ethylene carbonate and 1% of 1, 3-propane sultone by mass percent, and adding 0.8% of lithium difluorophosphate, 0.5% of lithium difluorosulfimide and 0.5% of lithium difluorophosphate by mass percent to prepare 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 this example is the same as that of example 1.
Example 9
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises 0.2% of tetraethynyl silane, 1% of vinyl sulfate, 0.5% of vinylene carbonate and 1% of 1, 3-propane sultone additive by mass percent based on 100% of the total mass of the nonaqueous electrolyte, wherein lithium salt comprises 1mol/L lithium hexafluorophosphate, 0.5% of lithium difluorosulfimide and 0.5% of lithium difluorophosphate by mass percent, and the balance of a nonaqueous solvent is composed of ethylene carbonate, ethylmethyl carbonate and diethyl carbonate according to a mass ratio of 3:5:2.
The preparation method of the nonaqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was formulated in a glove box where the nitrogen content was 99.999%, the actual oxygen content in the glove box was 0.1ppm, and the moisture content was 0.1ppm. And (3) uniformly mixing the ethylene carbonate, the ethylmethyl carbonate and the 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 tetraethynyl silane, 1% of ethylene sulfate, 0.5% of ethylene carbonate and 1% of 1, 3-propane sultone by mass percent, and adding 0.8% of lithium difluorophosphate, 0.5% of lithium difluorosulfimide and 0.5% of lithium difluorophosphate by mass percent to prepare 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 this example is the same as that of example 1.
Example 10
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises, based on 100% of the total mass of the nonaqueous electrolyte, 1% of tetraethynyl silane, 1% of vinyl sulfate, 0.5% of vinylene carbonate and 1% of an additive of 1, 3-propane sultone, wherein the lithium salt comprises 1mol/L lithium hexafluorophosphate, 0.8% of lithium difluorophosphate, 0.5% of lithium difluorosulfonimide and 0.5% of lithium difluorosulfonate, and the balance of a nonaqueous solvent, wherein the nonaqueous solvent consists of vinyl carbonate, methyl ethyl carbonate and diethyl carbonate in a mass ratio of 3:5:2.
The preparation method of the nonaqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was formulated in a glove box where the nitrogen content was 99.999%, the actual oxygen content in the glove box was 0.1ppm, and the moisture content was 0.1ppm. And (3) uniformly mixing the ethylene carbonate, the ethylmethyl carbonate and the 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% of tetraethynyl silane, 1% of ethylene sulfate, 0.5% of ethylene carbonate and 1% of 1, 3-propane sultone in percentage by mass, and adding 0.8% of lithium difluorophosphate, 0.5% of lithium difluorosulfimide and 0.5% of lithium difluorophosphate in percentage by mass respectively to obtain the concentration of lithium hexafluorophosphate of 1mol/L, thereby preparing the nonaqueous electrolyte of the lithium ion battery.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of this example is the same as that of example 1.
Example 11
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises 2.5% of tetraethynyl silane, 1% of vinyl sulfate, 0.5% of vinylene carbonate and 1% of 1, 3-propane sultone additive by mass percent based on 100% of the total mass of the nonaqueous electrolyte, wherein lithium salt comprises 1mol/L lithium hexafluorophosphate, 0.5% of lithium difluorosulfimide and 0.5% of lithium difluorophosphate by mass percent, and the balance of a nonaqueous solvent is composed of ethylene carbonate, ethylmethyl carbonate and diethyl carbonate according to a mass ratio of 3:5:2.
The preparation method of the nonaqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was formulated in a glove box where the nitrogen content was 99.999%, the actual oxygen content in the glove box was 0.1ppm, and the moisture content was 0.1ppm. And (3) uniformly mixing the ethylene carbonate, the ethylmethyl carbonate and the 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% of tetraethynyl silane, 1% of ethylene sulfate, 0.5% of ethylene carbonate and 1% of 1, 3-propane sultone by mass percent, and adding 0.8% of lithium difluorophosphate, 0.5% of lithium difluorosulfimide and 0.5% of lithium difluorophosphate by mass percent to prepare 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 this example is the same as that of example 1.
Example 12
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises 0.05% of tetravinyl siloxane, 0.05% of tetraethynyl silane, 1% of vinyl sulfate, 0.5% of vinylene carbonate and 1% of 1, 3-propane sultone additive in percentage by mass based on 100% of the total mass of the nonaqueous electrolyte, wherein the lithium salt comprises 1mol/L lithium hexafluorophosphate, 0.8% of lithium difluorophosphate, 0.5% of lithium difluorosulfimide and 0.5% of lithium difluorophosphate, and the balance of a nonaqueous solvent, wherein the nonaqueous solvent consists of vinyl carbonate, ethylmethyl carbonate and diethyl carbonate in a mass ratio of 3:5:2.
The preparation method of the nonaqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was formulated in a glove box where the nitrogen content was 99.999%, the actual oxygen content in the glove box was 0.1ppm, and the moisture content was 0.1ppm. The preparation method comprises the steps of uniformly mixing ethylene carbonate, methyl ethyl carbonate and diethyl carbonate battery-grade organic solvent in a mass ratio of 3:5:2 based on 100% of the total mass of the nonaqueous electrolyte, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding 0.05% of tetravinyl siloxane, 0.05% of tetraethynyl silane, 1% of ethylene sulfate, 0.5% of ethylene carbonate and 1% of 1, 3-propane sultone, and adding 0.8% of lithium difluorophosphate, 0.5% of lithium difluorosulfimide and 0.5% of lithium difluorophosphate in percentage by mass respectively, so that the concentration of lithium hexafluorophosphate is 1mol/L, and preparing the nonaqueous electrolyte of the lithium ion battery.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of this example is the same as that of example 1.
Example 13
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises 0.2% of tetravinyl siloxane, 0.2% of tetraethynyl silane, 1% of vinyl sulfate, 0.5% of vinylene carbonate and 1% of 1, 3-propane sultone additive in percentage by mass based on 100% of the total mass of the nonaqueous electrolyte, wherein the lithium salt comprises 1mol/L lithium hexafluorophosphate, 0.8% of lithium difluorophosphate, 0.5% of lithium difluorosulfimide and 0.5% of lithium difluorophosphate, and the balance of a nonaqueous solvent, wherein the nonaqueous solvent consists of vinyl carbonate, ethylmethyl carbonate and diethyl carbonate in a mass ratio of 3:5:2.
The preparation method of the nonaqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was formulated in a glove box where the nitrogen content was 99.999%, the actual oxygen content in the glove box was 0.1ppm, and the moisture content was 0.1ppm. The preparation method comprises the steps of uniformly mixing ethylene carbonate, methyl ethyl carbonate and diethyl carbonate battery-grade organic solvent in a mass ratio of 3:5:2 based on 100% of the total mass of the nonaqueous electrolyte, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding 0.2% of tetravinyl siloxane, 0.2% of tetraethynyl silane, 1% of ethylene sulfate, 0.5% of ethylene carbonate and 1% of 1, 3-propane sultone, and adding 0.8% of lithium difluorophosphate, 0.5% of lithium difluorosulfimide and 0.5% of lithium difluorophosphate in percentage by mass respectively, so that the concentration of lithium hexafluorophosphate is 1mol/L, and preparing the nonaqueous electrolyte of the lithium ion battery.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of this example is the same as that of example 1.
Example 14
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises, based on 100% of the total mass of the nonaqueous electrolyte, 1% of tetravinyl siloxane, 1% of tetraethynyl silane, 1% of vinyl sulfate, 0.5% of vinylene carbonate and 1% of 1, 3-propane sultone additive, wherein the lithium salt comprises 1mol/L lithium hexafluorophosphate, 0.8% of lithium difluorophosphate, 0.5% of lithium difluorosulfimide and 0.5% of lithium difluorophosphate, and the balance of nonaqueous solvent is composed of ethylene carbonate, methyl ethyl carbonate and diethyl carbonate in a mass ratio of 3:5:2.
The preparation method of the nonaqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was formulated in a glove box where the nitrogen content was 99.999%, the actual oxygen content in the glove box was 0.1ppm, and the moisture content was 0.1ppm. And (3) uniformly mixing ethylene carbonate, methyl ethyl carbonate and diethyl carbonate battery grade organic solvent in a mass ratio of 3:5:2 based on 100% of the total mass of the nonaqueous electrolyte, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding tetravinyl siloxane, tetraethynyl silane, vinyl sulfate, vinylene carbonate and 1, 3-propane sultone in a mass percentage of 1% respectively, and adding lithium difluorophosphate, lithium difluorosulfimide and lithium difluorophosphate in a mass percentage of 0.8% respectively, wherein the concentration of the lithium hexafluorophosphate is 1mol/L, so as to prepare the nonaqueous electrolyte of the lithium ion battery.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of this example is the same as that of example 1.
Example 15
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises, based on 100% of the total mass of the nonaqueous electrolyte, 2.5% of tetravinyl siloxane, 2.5% of tetraethynyl silane, 1% of vinyl sulfate, 0.5% of vinylene carbonate and 1% of 1, 3-propane sultone additive, wherein the lithium salt comprises 1mol/L of lithium hexafluorophosphate, 0.8% of lithium difluorophosphate, 0.5% of lithium difluorosulfimide and 0.5% of lithium difluorophosphate, and the balance of a nonaqueous solvent, wherein the nonaqueous solvent consists of vinyl carbonate, ethylmethyl carbonate and diethyl carbonate in a mass ratio of 3:5:2.
The preparation method of the nonaqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte was formulated in a glove box where the nitrogen content was 99.999%, the actual oxygen content in the glove box was 0.1ppm, and the moisture content was 0.1ppm. And (2) uniformly mixing ethylene carbonate, methyl ethyl carbonate and diethyl carbonate battery grade organic solvent according to the mass ratio of 3:5:2, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding tetravinyl siloxane, tetraethynyl silane, vinyl sulfate, ethylene carbonate and 1, 3-propane sultone with the mass percentage of 2.5% and 1, 3-propane sultone with the mass percentage of 0.5%, and adding lithium difluorophosphate, lithium difluorosulfimide and lithium difluorophosphate with the mass percentage of 0.5% respectively, so that the concentration of lithium hexafluorophosphate is 1mol/L, and preparing the nonaqueous electrolyte of the lithium ion battery.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of this example is the same as that of example 1.
Comparative example 1
The comparative example differs from example 4 in that the mass percentage of the tetravinyl siloxane was 25% based on 100% of the total mass of the nonaqueous electrolytic solution, and the total amount of the electrolytic solution was 100% by adaptively adjusting the amount of the nonaqueous solvent, and the other raw materials, the proportions and the mass percentages of the respective components were the same as in example 4.
Comparative example 2
The comparative example differs from example 8 in that the mass percentage of the tetraethynyl silane additive was 25% based on 100% of the total mass of the nonaqueous electrolytic solution, and the total amount of the electrolytic solution was 100% by adaptively adjusting the amount of the nonaqueous solvent, and the other raw materials, the proportions and the mass percentages of the respective components were the same as in example 8.
Comparative example 3
The comparative example differs from example 12 in that no additive of tetravinyl siloxane and tetraethynyl silane was added, and the amount of nonaqueous solvent was adaptively adjusted so that the total amount of the electrolyte was 100%, and the other raw materials, ratios, and mass percentages of the components were the same as in example 12.
Comparative example 4
The comparative example differs from example 12 in that the mass percentage of the tetravinyl siloxane additive was 20% and the mass percentage of the tetraethynyl silane additive was 20% based on 100% of the total mass of the nonaqueous electrolytic solution, and the total amount of the electrolytic solution was 100% by adaptively adjusting the amount of the nonaqueous solvent, and the other raw materials, the proportions, and the mass percentages of the respective components were the same as in example 12.
Test conditions
The lithium ion batteries prepared in examples 1 to 15 and comparative examples 1 to 4 were respectively subjected to high-temperature storage performance test by the following test methods:
The lithium ion battery was charged to 4.2V at a constant current of 1C at 25C, then charged at a constant voltage to a current of 0.05C, and the thickness of the lithium ion battery before storage was measured and recorded as D 0 . Then the battery in full charge state is put into a baking oven at 60 ℃ for 30 days, and the thickness after the storage is tested and recorded as D 1 The thickness expansion ratio with respect to the lithium ion battery before storage was calculated according to the following formula:
thickness expansion ratio (%) = (D) 1 -D 0 )/D 0 ×100％。
Charging the lithium ion battery to 4.2V at a constant current of 1C at 25 ℃, then charging to a current of less than 0.05C at a constant voltage of 4.2V, 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 marking as R 0 The method comprises the steps of carrying out a first treatment on the surface of the Charging to 4.2V with 1C constant current, charging to current less than 0.05C with 4.2V constant voltage, storing the lithium ion battery at 60deg.C for 30 days, and discharging to 3.0V with 1C constant current after storage; then charging to 4.2V with 1C constant current, then charging to current less than 0.05C with 4.2V constant voltage, then discharging to 3.0V with 0.5C constant current, testing discharge capacity of lithium ion battery at this time and marking as R 1 . The capacity retention rate with respect to the lithium ion battery before storage was calculated according to the following formula:
capacity retention (%) = (R) 1 /R 0 )×100％
The results of the test are shown in table 1:
Table 1:
as can be seen from the data in table 1, the present invention adopts the nonaqueous electrolyte containing the additive, and by testing the high-temperature storage performance of the lithium ion batteries prepared in the above examples 1 to 15, the lithium ion batteries show the best comprehensive performance when the mass content of the first compound additive in the nonaqueous electrolyte is 0.2%, wherein the capacity retention rate of the lithium ion batteries provided in examples 5, 9 and 13 is up to 94.6% or more, which further illustrates the advantages of high storage capacity retention rate and long cycle life of the lithium ion batteries prepared by adopting the electrolyte of the present invention; compared with comparative examples 1-4, the gas generation volume increase rate of the lithium ion batteries provided in examples 5, 9 and 13 at 60 ℃ is less than 6.5%, which indicates that the thickness increase of the lithium ion batteries in examples 5, 9 and 13 is far less than that of the lithium ion batteries in comparative examples 1-4, and further the electrolyte provided by the invention can relieve the volume expansion of the batteries, 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 optimal mass percent content exists when the tetravinyl siloxane additive is added, and when the mass percent content of the tetravinyl siloxane additive is 0.2% based on 100% of the total mass of the nonaqueous electrolyte, a relatively uniform and compact CEI film can be formed on the surface of the positive electrode material in the storage process of the electrolyte, so that the prepared lithium ion battery has excellent high-temperature storage stability.
Similarly, compared with examples 8-11, the electrolyte provided by the invention has the advantages that the optimal mass percent content exists when the tetraethynyl silane additive is added, and when the mass percent content of the added tetravinyl siloxane additive is 0.2% based on 100% of the total mass of the nonaqueous electrolyte, a relatively uniform and compact SEI film can be formed on the surface of the negative electrode material in the storage process, so that the prepared lithium ion battery has excellent high-temperature storage stability.
In summary, with comparative examples 12 to 15, when tetravinyl siloxane film-forming at the positive electrode and tetraethynyl silane film-forming at the negative electrode are simultaneously added, the high-temperature storage performance of the lithium ion battery may have more excellent performance.
Comparative examples 1, 2 and 4 illustrate that the addition of an excessively high amount of tetravinyl siloxane or tetraethynyl silane results in a thicker SEI film, an increased resistance of the battery, and an adverse effect on the electrochemical performance of the lithium ion battery; comparative example 3 shows that stable SEI films cannot be formed on the surfaces of the positive and negative electrodes of a lithium ion battery without adding tetravinyl siloxane and tetraethynyl silane, and thus may exhibit poor high temperature storage performance.
The applicant states that the process of the invention is illustrated by the above examples, but the invention is not limited to, i.e. does not mean that the invention must be carried out in dependence on the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (15)
1. A lithium ion battery nonaqueous electrolyte, comprising an electrolyte, a nonaqueous solvent, and an additive comprising a first compound, a cyclic ester additive, and a lithium salt additive:
the first compound includes a second compound having a structure shown in formula 2 and a third compound having a structure shown in formula 3:
the mass percentage of the first compound in the nonaqueous electrolyte of the lithium ion battery is 0.05 to 5 percent;
the mass percentage of the cyclic ester additive in the nonaqueous electrolyte of the lithium ion battery is 2.5-5%;
the lithium salt additive includes a combination of lithium difluorophosphate, and lithium difluorosulfonimide.
2. The lithium ion battery nonaqueous electrolyte according to claim 1, wherein the cyclic ester additive in the lithium ion battery nonaqueous electrolyte comprises any one or a combination of at least two of a cyclic carbonate additive, a cyclic sulfonate additive, or a cyclic sulfate additive.
3. The lithium ion battery nonaqueous electrolyte according to claim 2, wherein the cyclic carbonate-based additive comprises any one or a combination of at least two of vinylene carbonate, fluoroethylene carbonate, or ethylene carbonate.
4. The nonaqueous electrolyte for lithium ion batteries according to claim 2, wherein the cyclic sultone-based additive comprises any one or a combination of two of 1, 3-propane sultone and 1, 3-propenoic sultone.
5. The lithium ion battery nonaqueous electrolyte according to claim 2, wherein the cyclic sulfate-based additive comprises any one of vinyl sulfate, propylene sulfate, or a combination of at least two of them.
6. The lithium ion battery nonaqueous electrolyte of claim 1, wherein the electrolyte is a lithium salt.
7. The lithium ion battery nonaqueous electrolyte of claim 6, wherein the lithium salt comprises lithium hexafluorophosphate.
8. The lithium ion battery nonaqueous electrolyte according to claim 7, wherein a concentration of lithium hexafluorophosphate in the lithium ion battery nonaqueous electrolyte is 0.5mol/L to 2mol/L.
9. The lithium ion battery nonaqueous electrolyte according to claim 1, wherein the mass percentage of the lithium salt additive in the lithium ion battery nonaqueous electrolyte is 0.05% to 20%.
10. The lithium ion battery nonaqueous electrolyte according to claim 1, wherein the nonaqueous solvent comprises any one or a combination of at least two of ethylene carbonate, dimethyl carbonate, methylethyl carbonate, propylene carbonate, and diethyl carbonate.
11. The nonaqueous electrolyte for lithium ion batteries according to claim 1, wherein the nonaqueous solvent in the nonaqueous electrolyte for lithium ion batteries is 60% to 85% by mass.
12. A lithium ion battery characterized in that it comprises the lithium ion battery nonaqueous electrolyte according to any one of claims 1 to 11.
13. The lithium ion battery of claim 12, further comprising a positive current collector and a positive active material coated on the positive current collector, a negative current collector and a negative active material coated on the negative current collector, and a separator.
14. The lithium ion battery of claim 13, wherein the positive electrode active material comprises 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.
15. The lithium ion battery of claim 13, wherein the negative electrode active material comprises any one or a combination of at least two of soft carbon, hard carbon, artificial graphite, natural graphite, silicon, a silicon oxygen compound, a silicon carbon compound, or lithium titanate.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070030682A (en) * | 2005-09-13 | 2007-03-16 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Cyclic Carbonate-Modified Organosilicon Compound, Non-Aqueous Electrolytic Solution Comprising the Same, Secondary Battery and Capacitor |
| JP2009245922A (en) * | 2008-03-13 | 2009-10-22 | Hitachi Maxell Ltd | Nonaqueous electrolyte secondary battery |
| CN109921092A (en) * | 2019-03-06 | 2019-06-21 | 杉杉新材料（衢州）有限公司 | A kind of silicon-based anode non-aqueous electrolyte for lithium ion cell and the silicon-based anode lithium ion battery containing the electrolyte |
| CN113054250A (en) * | 2019-12-27 | 2021-06-29 | 张家港市国泰华荣化工新材料有限公司 | Electrolyte and lithium ion battery |
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| JP5029809B2 (en) * | 2007-01-15 | 2012-09-19 | 信越化学工業株式会社 | Non-aqueous electrolyte and secondary battery using the same |
| CN103367804B (en) * | 2013-06-27 | 2015-11-18 | 深圳新宙邦科技股份有限公司 | A kind of lithium ion battery nonaqueous electrolytic solution and use the lithium ion battery of this nonaqueous electrolytic solution |
| CN112002944B (en) * | 2020-09-25 | 2022-04-29 | 天目湖先进储能技术研究院有限公司 | High-temperature electrolyte for silicon-carbon composite cathode and secondary battery |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070030682A (en) * | 2005-09-13 | 2007-03-16 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Cyclic Carbonate-Modified Organosilicon Compound, Non-Aqueous Electrolytic Solution Comprising the Same, Secondary Battery and Capacitor |
| JP2009245922A (en) * | 2008-03-13 | 2009-10-22 | Hitachi Maxell Ltd | Nonaqueous electrolyte secondary battery |
| CN109921092A (en) * | 2019-03-06 | 2019-06-21 | 杉杉新材料（衢州）有限公司 | A kind of silicon-based anode non-aqueous electrolyte for lithium ion cell and the silicon-based anode lithium ion battery containing the electrolyte |
| CN113054250A (en) * | 2019-12-27 | 2021-06-29 | 张家港市国泰华荣化工新材料有限公司 | Electrolyte and lithium ion battery |
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