CN114447435A - Non-aqueous electrolyte for lithium secondary battery and preparation method and application thereof - Google Patents
Non-aqueous electrolyte for lithium secondary battery and preparation method and application thereof Download PDFInfo
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- secondary battery
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 37
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 34
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 23
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 23
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims abstract description 22
- ISQPYTOJCDIYBW-UHFFFAOYSA-N tris(ethenyl)-[2-tris(ethenyl)silylethyl]silane Chemical compound C=C[Si](C=C)(C=C)CC[Si](C=C)(C=C)C=C ISQPYTOJCDIYBW-UHFFFAOYSA-N 0.000 claims description 17
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 7
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 6
- 229910012265 LiPO2F2 Inorganic materials 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 229910003253 LiB10Cl10 Inorganic materials 0.000 claims description 2
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 2
- 239000003759 ester based solvent Substances 0.000 claims description 2
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 claims description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000014759 maintenance of location Effects 0.000 abstract description 7
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- UFHILTCGAOPTOV-UHFFFAOYSA-N tetrakis(ethenyl)silane Chemical compound C=C[Si](C=C)(C=C)C=C UFHILTCGAOPTOV-UHFFFAOYSA-N 0.000 description 5
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000002482 conductive additive Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 102000004310 Ion Channels Human genes 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910004427 Li(Ni0.7Mn0.15Co0.15)O2 Inorganic materials 0.000 description 1
- 229910004437 Li(Ni0.8Mn0.1Co0.1)O2 Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
Abstract
The invention provides a non-aqueous electrolyte for a lithium secondary battery, and a preparation method and application thereof, wherein the non-aqueous electrolyte comprises 1, 2-bis (trivinyl silicon-based) ethane, lithium salt and an ester solvent. The nonaqueous electrolytic solution of the present invention has improved cycle life and capacity retention.
Description
Technical Field
The invention belongs to the technical field of lithium secondary batteries, and particularly relates to a non-aqueous electrolyte for a lithium secondary battery, and a preparation method and application thereof.
Background
Lithium secondary batteries have high energy density and high operating voltage, and have been widely used in mobile terminal products such as mobile phones, notebook computers, tablet computers, and the like. Also, in consideration of environmental protection, new energy vehicles are rapidly developed under the push of governments and vehicle manufacturers of various countries, and lithium secondary batteries are an ideal power source for new generation electric vehicles by virtue of their excellent performance.
In the lithium secondary battery, lithium ions react with an electrolyte solution in a voltage range of 0.5 to 3.5V during initial charging, and a passivation layer, namely a Solid Electrolyte Interface (SEI) is formed on the surface of a negative electrode. The SEI film may prevent lithium ions from reacting with an anode material such as a carbon anode or other materials during charge and discharge, and may serve as an Ion channel (Ion Tunnel) through which lithium ions pass. Since the ion channel can prevent structural damage of the carbon negative electrode due to co-intercalation of the carbon negative electrode with a non-aqueous organic solvent having a high molecular weight, cycle life and output characteristics of the lithium secondary battery are improved. Therefore, the SEI film has an important influence on the performance of the lithium secondary battery, particularly, the cycle performance and the energy storage characteristic.
Chinese patent application CN109075387A discloses a non-aqueous electrolyte solution for a lithium secondary battery, which comprises 1: 3-20 weight ratio of tetravinylsilane, lithium difluorophosphate and 1, 3-allyl sulfate as mixed additives, wherein the addition amount of the mixed additives is 1-4 wt%, particularly 1.8-4 wt%, so as to form a stable solid electrolyte interface film on the surface of a negative electrode, and further improve the high-temperature storage property and the cycle life of the lithium secondary battery.
However, it is still desirable to provide a nonaqueous electrolytic solution for a lithium secondary battery having an improved cycle life.
Disclosure of Invention
In view of this, the present invention provides a nonaqueous electrolyte for a lithium secondary battery, which has improved cycle life and capacity retention rate, and a method for preparing the same and applications thereof.
The purpose of the invention is realized by the following technical scheme.
In a first aspect, the present invention provides a nonaqueous electrolyte for a lithium secondary battery, wherein the nonaqueous electrolyte includes 1, 2-bis (trivinylsilyl) ethane, a lithium salt, and an ester solvent.
The inventors of the present application have found that the cycle life and capacity retention of a lithium secondary battery can be improved by adding 1, 2-bis (trivinylsilyl) ethane to a nonaqueous electrolytic solution. Without wishing to be bound by theory, it is believed that 1, 2-bis (trivinylsilyl) ethane may participate in the formation of the SEI film and contain more vinyl groups per molecule than tetravinylsilane (as shown in formula II), and the residual vinyl groups may prevent the destruction of the SEI film due to the steric hindrance during the formation of the SEI film, and the residual vinyl groups may remain partially vinyl groups. In addition, it is considered that 1, 2-bis (trivinylsilyl) ethane has a higher boiling point (267 ℃ C. at 760 mmHg) and a low vapor pressure (0.0138 mmHg at 25 ℃ C.) and can further reduce the generation of gas during the SEI film formation, resulting in a more stable SEI film.
The nonaqueous electrolyte provided by the invention is characterized in that the structure of 1, 2-bis (trivinylsilyl) ethane is shown as the formula I:
the nonaqueous electrolyte provided by the invention comprises 0.05-1 wt% of 1, 2-bis (trivinylsilyl) ethane. For example, the content of 1, 2-bis (trivinylsilyl) ethane in the nonaqueous electrolytic solution may be 0.05 wt%, 0.1 wt%, 0.15 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, or a range consisting of them.
In some embodiments, the amount of 1, 2-bis (trivinylsilyl) ethane in the nonaqueous electrolytic solution is 0.1 to 0.8% by weight; in some embodiments from 0.2 to 0.8 wt%; and in some embodiments from 0.4 to 0.6 wt%.
According to the nonaqueous electrolytic solution provided by the present invention, wherein the lithium salt is not particularly required in the present invention, any known lithium salt in the art may be used. For example, the lithium salt may be an inorganic lithium salt and/or an organic lithium salt.
Examples of inorganic lithium salts suitable for use in the present invention include, but are not limited to: LiCl, LiBr, LiI, LiClO4、LiBF4、LiB10Cl10、LiPF6、LiPO2F2、LiAsF6、LiSbF6And LiAlCl4。
Suitable for use in the present inventionExamples of organic lithium salts include, but are not limited to: LiCF3SO3、LiCH3CO2、LiCF3CO2And [ (CF)3)2CHOSO2]2NLi。
According to the nonaqueous electrolytic solution provided by the invention, the concentration of the lithium salt in the nonaqueous electrolytic solution can be 0.1-2 mol/L. For example, the concentration of the lithium salt in the nonaqueous electrolytic solution may be 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1mol/L, 1.2mol/L, 1.5mol/L, 1.8mol/L, 2mol/L or a range consisting of them.
In some embodiments, the concentration of the lithium salt in the nonaqueous electrolytic solution is 0.1 to 1.5 mol/L; and in some embodiments from 0.8 to 1.2 mol/L.
According to the present invention, there is provided a nonaqueous electrolytic solution, wherein the lithium salt includes LiPF6And LiPO2F2And/or [ (CF)3)2CHOSO2]2NLi, the concentration of the lithium salt is 0.8-1.2 mol/L, and LiPF6With LiPO2F2And/or [ (CF)3)2CHOSO2]2Mass ratio of NLi is 1: 0.01 to 0.03.
According to the nonaqueous electrolytic solution provided by the invention, the ester solvent comprises an aprotic carbonate solvent.
Examples of aprotic carbonate solvents suitable for use in the present invention include, but are not limited to: propylene Carbonate (PC), Ethylene Carbonate (EC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC).
In some embodiments, the ester-based solvent includes a first aprotic carbonate solvent selected from at least one of Propylene Carbonate (PC) and Ethylene Carbonate (EC) and a second aprotic carbonate solvent selected from at least one of diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), and dimethyl carbonate (DMC) in a mass ratio of 1.5 to 3:1, preferably 1.5 to 2: 1.
In some preferred embodiments, the ester solvent includes Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC) in a mass ratio of 1.5 to 3:1, preferably 1.5 to 2: 1.
The non-aqueous electrolyte provided by the invention can further comprise an additive selected from Vinylene Carbonate (VC) and Vinyl Ethylene Carbonate (VEC). It is considered that Vinylene Carbonate (VC) and Vinyl Ethylene Carbonate (VEC) can further improve the capacity retention rate of the lithium secondary battery.
In some embodiments, the additive is present in an amount of 0.6 to 0.8 wt% based on the weight of the nonaqueous electrolytic solution.
In a second aspect, the present invention provides a method for preparing a nonaqueous electrolytic solution, wherein the method comprises the steps of: 1, 2-bis (trivinylsilyl) ethane, a lithium salt and optional additives are mixed with an ester solvent.
In a third aspect, the present invention provides the use of a nonaqueous electrolytic solution in a lithium secondary battery.
In a fourth aspect, the present invention provides a lithium secondary battery, wherein the lithium secondary battery comprises a positive electrode, a negative electrode, a separator, and the nonaqueous electrolytic solution.
In the present invention, the cathode, anode and separator may employ any cathode, anode and separator materials known in the art, and the present invention is not particularly limited thereto.
According to the lithium secondary battery provided by the present invention, the positive electrode may include a positive electrode current collector and a positive electrode active material supported on the positive electrode current collector.
The positive current collecting plate suitable for the lithium secondary battery of the present invention includes, but is not limited to: aluminum foil collector plates and calcined carbon.
Examples of the positive active material suitable for the lithium secondary battery of the present invention include, but are not limited to: lithium iron phosphate, Li (Ni)0.6Mn0.2Co0.2)O2、Li(Ni0.7Mn0.15Co0.15)O2、Li(Ni0.8Mn0.1Co0.1)O2And LiCoO2。
According to the lithium secondary battery provided by the present invention, the positive electrode may further include a conductive additive and a binder.
The conductive additive is not particularly limited in the present invention, and any known electrical additive in the art may be used. In some embodiments, the conductive additive is carbon black.
Also, the adhesive is not particularly limited in the present invention, and any adhesive known in the art may be used. In some embodiments, the binder is polyvinylidene fluoride (PVDF).
According to the lithium secondary battery provided by the present invention, the negative electrode may be metallic lithium or graphite.
According to the lithium secondary battery provided by the invention, the diaphragm is a PP/PE/PP three-layer film with two sides coated with alumina.
The invention has the following advantages:
(1) the nonaqueous electrolytic solution of the present invention has improved cycle life and capacity retention. Without wishing to be bound by theory, it is believed that 1, 2-bis (trivinylsilyl) ethane may participate in the formation of an SEI film, and contains more vinyl groups per molecule than tetravinylsilane, and the residual vinyl groups may prevent the destruction of the SEI film due to the residual vinyl groups, which are caused by steric hindrance, during the formation of the SEI film. In addition, it is considered that 1, 2-bis (trivinylsilyl) ethane, which has a higher boiling point (267 ℃ C. at 760 mmHg) and a low vapor pressure (0.0138 mmHg at 25 ℃ C.), can further reduce the generation of gas during the SEI film formation, resulting in the formation of a more stable SEI film.
(2) The lithium secondary battery of the invention can be used as an energy source for electric tools, electric bicycles, hybrid electric vehicles, pure electric vehicles and the like, and has wide application range and long service life.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The compounds which may be mentioned in the following examples and comparative examples and their abbreviations are as follows: tetravinylsilane (TVS), 1, 2-bis (trivinylsilyl) ethane (compound of formula I), lithium hexafluorophosphate (LiPF)6) Lithium difluorophosphate (LiPO)2F2) Ethylene Carbonate (EC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), Vinylene Carbonate (VC), and N-methyl-2-pyrrolidone (NMP). In addition, the chemicals and raw materials referred to in the following examples are all commercially available.
Examples 1 to 10
A nonaqueous electrolytic solution was prepared by mixing 1, 2-bis (trivinylsilyl) ethane, a lithium salt and optionally an additive with an ester solvent according to the formulation shown in table 1.
Comparative examples 1 to 3
A nonaqueous electrolytic solution was prepared by mixing 1, 2-bis (trivinylsilyl) ethane, a lithium salt and optionally an additive with an ester solvent according to the formulation shown in table 1.
TABLE 1
Performance testing
1. Preparation of lithium Secondary Battery
A positive electrode active material (Li (Ni))0.6Mn0.2Co0.2)O2) Carbon black as a conductive additive and polyvinylidene fluoride as a binder are dispersed in N-methyl-2-pyrrolidone (NMP) according to a weight ratio of 80:10:10, and are uniformly mixed to prepare positive electrode slurry. Coating the positive electrode slurry on an aluminum foil current collector with the thickness of 20 mu m, drying at 55 ℃ to form a pole piece with the thickness of 100 mu m, and placing the pole piece on a roller press to press(pressure about 1MPa × 1.5 cm)2) Cutting the anode plate into round pieces with the diameter, then placing the round pieces in a vacuum oven to be dried for 6 hours at the temperature of 120 ℃, naturally cooling the round pieces, taking out the round pieces and placing the round pieces in a glove box to be used as anode plates.
In a glove box filled with nitrogen atmosphere, metal lithium is used as the negative electrode of the battery, a PP/PE/PP three-layer film with two sides coated with alumina is used as a diaphragm and is placed between the positive electrode and the negative electrode, a non-aqueous electrolyte is dripped, the prepared positive electrode piece is used as the positive electrode, and the button battery with the model CR2032 is assembled.
2. High temperature storage Performance test
After storing the lithium secondary battery at a high temperature of 60 ℃ for 16 weeks, it was charged to 4.25V/55mA at 1C under a constant current/constant voltage (CC/CV) condition at room temperature, and then discharged to a voltage of 2.5V at a Constant Current (CC) of 2C, and the capacity retention rate after high-temperature storage was measured by calculating the discharge capacity after 16 weeks as a percentage (capacity after 16 weeks/initial discharge capacity × 100 (%)). The results are shown in Table 2.
3. Cycle life test
The lithium secondary battery was charged to 4.25V/55mA at 45 ℃ under a constant current/constant voltage (CC/CV) condition at 1C, and then discharged to a voltage of 3.0V (100 cycles/1 cycle × 100%) at a Constant Current (CC) of 2C to measure the lifetime of 100 cycles at high temperature, and the results are shown in table 2.
The lithium secondary battery was charged to 4.25V/55mA at 25 ℃ under a constant current/constant voltage (CC/CV) condition at 1C, and then discharged to a voltage of 3.0V (100 cycles/1 cycle × 100%) at a Constant Current (CC) of 2C to measure the lifetime of 100 cycles at room temperature, and the results are shown in table 2.
TABLE 2 lithium Secondary Battery Performance
As can be seen from table 2, the nonaqueous electrolytic solution of the present invention has improved cycle life and improved capacity retention.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A nonaqueous electrolyte for a lithium secondary battery, wherein the nonaqueous electrolyte includes 1, 2-bis (trivinylsilyl) ethane, a lithium salt, and an ester solvent.
2. The nonaqueous electrolytic solution of claim 1, wherein the nonaqueous electrolytic solution contains 1, 2-bis (trivinylsilyl) ethane in an amount of 0.05 to 1 wt%, preferably 0.1 to 0.8 wt%, more preferably 0.2 to 0.8 wt%, and most preferably 0.4 to 0.6 wt%.
3. The nonaqueous electrolytic solution of claim 1 or 2, wherein the lithium salt is selected from LiCl, LiBr, LiI, LiClO4、LiBF4、LiB10Cl10、LiPF6、LiPO2F2、LiAsF6、LiSbF6、LiAlCl4、LiCF3SO3、LiCH3CO2、LiCF3CO2And [ (CF)3)2CHOSO2]2At least one of NLi; and/or
The concentration of the lithium salt in the nonaqueous electrolytic solution is 0.1 to 2mol/L, preferably 0.1 to 1.5mol/L, and more preferably 0.8 to 1.2 mol/L.
4. The nonaqueous electrolytic solution of claim 3, wherein the lithium salt comprises LiPF6And LiPO2F2And/or [ (CF)3)2CHOSO2]2NLi, the concentration of the lithium salt is 0.8-1.2 mol/L, and LiPF6With LiPO2F2And/or [ (CF)3)2CHOSO2]2Mass ratio of NLi is 1: 0.01 to 0.03.
5. The nonaqueous electrolytic solution of any one of claims 1 to 4, wherein the ester-based solvent includes at least one selected from the group consisting of propylene carbonate, ethylene carbonate, diethyl carbonate, ethyl methyl carbonate, and dimethyl carbonate.
6. The nonaqueous electrolytic solution according to any one of claims 1 to 4, wherein the ester solvent includes a first aprotic carbonate solvent and a second aprotic carbonate solvent in a mass ratio of 1.5 to 3:1, preferably 1.5 to 2:1, the first aprotic carbonate solvent being selected from at least one of propylene carbonate and ethylene carbonate, the second aprotic carbonate solvent being selected from at least one of diethyl carbonate, ethyl methyl carbonate, and dimethyl carbonate;
preferably, the ester solvent comprises ethylene carbonate and methyl ethyl carbonate in a mass ratio of 1.5-3: 1, preferably 1.5-2: 1.
7. The nonaqueous electrolytic solution of any one of claims 1 to 6, wherein the nonaqueous electrolytic solution may further include an additive selected from vinylene carbonate and ethylene carbonate;
preferably, the content of the additive is 0.6 to 0.8 wt% based on the weight of the nonaqueous electrolytic solution.
8. The method for producing the nonaqueous electrolytic solution of any one of claims 1 to 7, wherein the method for producing comprises the steps of: 1, 2-bis (trivinylsilyl) ethane, a lithium salt and optional additives are mixed with an ester solvent.
9. Use of the nonaqueous electrolytic solution of any one of claims 1 to 7 in a lithium secondary battery.
10. A lithium secondary battery comprising a positive electrode, a negative electrode, a separator and the nonaqueous electrolytic solution of any one of claims 1 to 7.
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