CN113410510A - Lithium ion battery - Google Patents

Lithium ion battery Download PDF

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Publication number
CN113410510A
CN113410510A CN202110632599.0A CN202110632599A CN113410510A CN 113410510 A CN113410510 A CN 113410510A CN 202110632599 A CN202110632599 A CN 202110632599A CN 113410510 A CN113410510 A CN 113410510A
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glue
lithium ion
ion battery
layer
coated
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母英迪
张祖来
王海
李素丽
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Zhuhai Cosmx Battery Co Ltd
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Zhuhai Cosmx Battery Co Ltd
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Priority to PCT/CN2022/096946 priority patent/WO2022257859A1/en
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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
    • 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
    • H01M10/056—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
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • 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
    • 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

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Abstract

The invention provides a lithium ion battery, which is prepared by combining a diaphragm and an electrolyte under the combination of a positive electrode material and a negative electrode material through the synergistic effect of the diaphragm and the electrolyte, and can effectively improve the safety performance of a battery core and simultaneously give consideration to the low-temperature performance of the battery core. The lithium ion battery comprises a non-aqueous electrolyte; the non-aqueous electrolyte comprises a non-aqueous organic solvent, an additive and a lithium salt, wherein the battery core has high and low temperature performance under the synergistic effect of the additive and the solvent in the electrolyte formula, and a thicker and stable CEI protective film can be formed on the surface of the positive electrode by combining tris (2-cyanoethyl) borate and the trimethylsilyl substituted methylsulfonamide compound shown in the formula 1, so that the stability of the positive electrode material under high temperature and high voltage is improved, the electrolyte is prevented from being oxidized on the surface of the positive electrode, and the heat release of side reactions is reduced.

Description

Lithium ion battery
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a high-voltage lithium ion battery with high safety performance.
Background
In recent years, lithium ion batteries have been widely used in the fields of smart phones, tablet computers, smart wearing, electric tools, electric automobiles, and the like. With the wide application of lithium ion batteries, the use environment and the demand of consumers on the lithium ion batteries are continuously improved, which requires that the lithium ion batteries have high safety while having high and low temperature performances.
At present, the lithium ion battery has potential safety hazards in the use process, for example, serious safety accidents, fire and even explosion easily occur under some extreme use conditions such as continuous high temperature and the like. The main reasons for these problems are that the positive electrode material is unstable in structure at high temperature and high voltage, and metal ions are easily dissolved out from the positive electrode and reduced and deposited on the surface of the negative electrode, so that the structure of the SEI film of the negative electrode is damaged, the impedance of the negative electrode and the thickness of the battery are continuously increased, the temperature of a battery core is continuously increased, and heat is continuously accumulated and cannot be released to cause safety accidents; on the other hand, the electrolyte is easy to decompose at high temperature and high voltage, and the electrolyte is easy to be oxidized and decomposed on the surface of the positive electrode to generate a large amount of gas, so that the battery bulges and the electrode interface is damaged, and the safety performance of the battery is obviously poor.
Under these circumstances, there is an urgent need to develop a high-voltage lithium ion battery having high safety, for example, safety performance can be improved by adding a flame retardant (such as trimethyl phosphate) to an electrolyte, but the use of these additives often causes severe deterioration of battery performance. Therefore, the development of a high-voltage lithium ion battery with high safety without affecting the electrochemical performance of the battery is a current primary task.
Disclosure of Invention
The invention aims to solve the problems that potential safety hazards exist in the use process of the conventional lithium ion battery, the safety performance of a battery cell and the electrochemical performance cannot be considered simultaneously, and the like, and provides a high-voltage lithium ion battery with high safety performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a lithium ion battery comprises a positive plate, a negative plate, a diaphragm arranged between the positive plate and the negative plate, and a non-aqueous electrolyte;
the diaphragm comprises a substrate, a ceramic layer, a first glue coating layer and a second glue coating layer, wherein the ceramic layer is coated on a first surface of the substrate, the first glue coating layer is coated on a second surface of the substrate, which is opposite to the first surface, and the second glue coating layer is coated on the surface of the ceramic layer;
the nonaqueous electrolyte comprises a nonaqueous organic solvent, an additive and a lithium salt, wherein the nonaqueous organic solvent comprises ethyl propionate; the additive comprises 4-methyl-1, 2-oxathiolane-2, 2-dioxide, tri (2-cyanoethyl) borate and at least one trimethylsilyl substituted methanesulfonamide compound shown as formula 1;
Figure BDA0003104241080000021
in formula 1, R is selected from aryl or
Figure BDA0003104241080000022
n is an integer between 1 and 6, and is a connecting point.
According to the invention, R is selected from C6-12Aryl (e.g. phenyl) or
Figure BDA0003104241080000023
n is an integer of 1 to 3 (e.g.
Figure BDA0003104241080000031
) Is a connection point.
According to the invention, the CAS number of the 4-methyl-1, 2-oxathiolane-2, 2-dioxide is 15606-89-0; the CAS number of the tris (2-cyanoethyl) borate is 126755-67-7.
According to the present invention, the additives can be prepared by methods known in the art, or can be obtained after being purchased commercially.
According to the present invention, the trimethylsilyl-substituted methanesulfonamide compound represented by formula 1 is at least one selected from the group consisting of the following formulas 1 to 1 and 1 to 2:
Figure BDA0003104241080000032
according to the invention, the 4-methyl-1, 2-oxathiolane-2, 2-dioxide is added in an amount of 1 to 3 wt.%, for example 1 wt.%, 1.2 wt.%, 1.4 wt.%, 1.5 wt.%, 1.8 wt.%, 2 wt.%, 2.2 wt.%, 2.5 wt.%, 2.8 wt.% or 3 wt.%, based on the total mass of the nonaqueous electrolyte.
According to the present invention, the tris (2-cyanoethyl) borate is added in an amount of 0.5 to 3.5 wt.%, for example, 0.5 wt.%, 0.6 wt.%, 0.8 wt.%, 0.9 wt.%, 1 wt.%, 1.2 wt.%, 1.4 wt.%, 1.5 wt.%, 1.8 wt.%, 2 wt.%, 2.2 wt.%, 2.5 wt.%, 2.8 wt.%, 3 wt.%, 3.2 wt.%, 3.4 wt.%, or 3.5 wt.%, based on the total mass of the nonaqueous electrolyte.
According to the present invention, the trimethylsilyl-substituted methanesulfonamide compound represented by formula 1 is added in an amount of 0.2 to 1.8 wt.%, for example, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.8 wt.%, 0.9 wt.%, 1 wt.%, 1.2 wt.%, 1.3 wt.%, 1.4 wt.%, 1.5 wt.%, 1.6 wt.%, 1.7 wt.%, or 1.8 wt.% based on the total mass of the nonaqueous electrolytic solution.
According to the invention, the ethyl propionate is added in an amount of 10 to 50 wt.%, preferably 20 to 40 wt.%, for example 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.% or 50 wt.%, based on the total mass of the nonaqueous electrolyte.
According to the present invention, the non-aqueous organic solvent further comprises at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl propionate and propyl acetate.
According to the invention, the lithium salt is at least one selected from lithium bistrifluoromethylsulfonyl imide, lithium bifluorosulfonimide and lithium hexafluorophosphate, and accounts for 13-20 wt% of the total mass of the nonaqueous electrolytic solution.
According to the invention, the nonaqueous electrolytic solution further comprises at least one of ethylene carbonate, 1, 3-propane sultone, ethylene glycol bis (propionitrile) ether, 1,2, 3-tris (2-cyanoethoxy) propane, lithium bis (oxalato) borate and lithium difluoro (oxalato) borate; the content of the non-aqueous electrolyte is 0-10 wt.%.
According to the invention, the substrate is selected from one or more of polyethylene, polypropylene, polyimide, polyamide and aramid.
According to the invention, the ceramic layer comprises a ceramic, a binder and a thickener.
According to the invention, the ceramic is selected from one or more of alumina, boehmite, magnesium oxide and magnesium hydroxide.
According to the invention, the binder is selected from one or more of polytetrafluoroethylene, polyvinylidene fluoride-hexafluoropropylene modification and copolymer thereof, polyimide, polyacrylonitrile and polymethyl methacrylate.
According to the invention, the thickening agent is selected from one or two of sodium carboxymethyl cellulose and lithium carboxymethyl cellulose.
According to the invention, the ceramic layer comprises the following components in percentage by mass: 85-97 wt% of ceramic, 1-10 wt% of binder and 0.5-10 wt% of thickener.
According to the invention, the first glue layer comprises a plurality of first glue areas and first non-glue areas which are arranged adjacent to each other, the first glue areas are coated with first glue, and the first non-glue areas are not coated with first glue. Illustratively, the first glue layer comprises a first glue area, a first non-glue area, a first non-glue area … … first glue area, which are adjacently arranged in sequence.
According to the invention, the second glue coating layer comprises a plurality of second glue coating areas and second non-glue coating areas which are arranged adjacent to each other, wherein the second glue coating areas are coated with second glue, and the second non-glue coating areas are not coated with the second glue. Illustratively, the second glue layer comprises a second glue area, a second non-glue area, a second glue area, and a second non-glue area … … which are adjacently arranged in sequence.
According to the invention, the first glue comprises one or more of polytetrafluoroethylene, polyvinylidene fluoride-hexafluoropropylene modified and copolymer thereof, polyimide, polyacrylonitrile and polymethyl methacrylate.
According to the invention, the second glue comprises one or more of polytetrafluoroethylene, polyvinylidene fluoride-hexafluoropropylene modified and copolymer thereof, polyimide, polyacrylonitrile and polymethyl methacrylate.
According to the invention, said first glue and said second glue are identical or different, preferably identical.
According to the invention, the first glue coating layer is non-full-coverage coating, namely a first glue coating area and a first non-glue coating area are arranged adjacent to each other, the width of the first glue coating area is 1-5 mm, and the width of the first non-glue coating area is 0.5-2 mm.
According to the invention, the second glue coating layer is non-full-coverage coating, namely a second glue coating area and a second non-glue coating area are arranged adjacent to each other, the width of the second glue coating area is 1-5 mm, and the width of the second non-glue coating area is 0.5-2 mm.
According to the invention, the thickness of the substrate is 5 to 20 μm, for example 5 μm, 8 μm, 10 μm, 15 μm, 18 μm or 20 μm.
According to the invention, the thickness of the ceramic layer is 1 to 5 μm, for example 1 μm, 2 μm, 3 μm, 4 μm or 5 μm.
According to the invention, the thickness of the first glue layer is 0.5-2 μm, such as 0.5 μm, 0.8 μm, 1 μm, 1.2 μm, 1.5 μm, 1.8 μm or 2 μm.
According to the invention, the thickness of the second glue layer is 0.5-2 μm, for example 0.5 μm, 0.8 μm, 1 μm, 1.2 μm, 1.5 μm, 1.8 μm or 2 μm.
According to the invention, the positive plate comprises a positive current collector and a positive active material layer coated on one side or two sides of the positive current collector, wherein the positive active material layer comprises a positive active material, a conductive agent and a binder.
According to the present invention, the negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer coated on one or both surfaces of the negative electrode current collector, the negative electrode active material layer including a negative electrode active material, a conductive agent, and a binder.
According to the invention, the positive active material is selected from lithium cobaltate or lithium cobaltate subjected to doping coating treatment of two or more elements of Al, Mg, Mn, Cr, Ti and Zr, and the chemical formula of the lithium cobaltate subjected to doping coating treatment of two or more elements of Al, Mg, Mn, Cr, Ti and Zr is LixCo1-y1-y2-y3-y4Ay1By2Cy3Dy4O2(ii) a X is more than or equal to 0.95 and less than or equal to 1.05, y1 is more than or equal to 0.01 and less than or equal to 0.1, y2 is more than or equal to 0.01 and less than or equal to 0.1, y3 is more than or equal to 0.1, y4 is more than or equal to 0 and less than or equal to 0.1, and A, B, C, D is selected from two or more elements of Al, Mg, Mn, Cr, Ti and Zr.
According to the invention, the lithium cobaltate subjected to doping coating treatment of two or more elements of Al, Mg, Mn, Cr, Ti and Zr has a median particle diameter D5010 to 17 μm, and a specific surface area BET of 0.15 to 0.45m2/g。
According to the invention, the negative active material is selected from graphite or a graphite composite material containing 1-12 wt.% SiOx/C or Si/C, wherein 0< x < 2.
According to the present invention, the charge cut-off voltage of the lithium ion battery is 4.45V or more.
The invention has the beneficial effects that:
the invention provides a high-voltage lithium ion battery with high safety performance.
The lithium ion battery prepared by the combination of the positive and negative electrode materials under the synergistic effect of the diaphragm and the electrolyte can effectively improve the safety performance of the battery core and simultaneously give consideration to the low-temperature performance of the battery core.
The lithium ion battery comprises a non-aqueous electrolyte; the non-aqueous electrolyte comprises a non-aqueous organic solvent, an additive and a lithium salt, the synergistic effect of the additive and the solvent in the electrolyte formula enables the cell to have high and low temperature performance, wherein the tri (2-cyanoethyl) borate and the trimethylsilyl substituted methylsulfonamide compound shown in the formula 1 can jointly form a thicker and stable CEI protective film on the surface of the positive electrode, the stability of the positive electrode material under high temperature and high voltage is improved, the electrolyte is prevented from being oxidized on the surface of the positive electrode, and the heat release of side reactions is reduced; meanwhile, 4-methyl-1, 2-oxathiolane-2, 2-dioxide and the trimethylsilyl substituted methylsulfonamide compound shown in the formula 1 can form a firm SEI film with high impedance on the surface of the negative electrode, so that the electrolyte is prevented from being reduced on the surface of the negative electrode, the self-discharge of the battery is prevented, and the high-temperature resistance of the electric core is improved. Meanwhile, the non-aqueous electrolyte is added with ethyl propionate with higher content, so that the viscosity of a solvent can be reduced, the wettability and the ionic conductivity of the electrolyte can be improved, and the low-temperature performance of a battery cell can be improved.
However, because a large amount of ethyl propionate is added into the electrolyte, the ethyl propionate has a low boiling point and high activity, is unstable in the battery core and is easily oxidized, reduced and decomposed by active substances, so that a large amount of heat is emitted in the reaction to cause the failure of the safety performance of the battery.
Drawings
FIG. 1: the cross section of the diaphragm in the lithium ion battery is schematic.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Comparative examples 1 to 5 and examples 1 to 8
The lithium ion batteries of comparative examples 1 to 5 and examples 1 to 8 were manufactured according to the following manufacturing method, except for the selection of the separator and the electrolyte, and the specific differences are shown in table 1.
(1) Preparation of positive plate
LiCoO as positive electrode active material2Mixing polyvinylidene fluoride (PVDF) serving as a binder and acetylene black serving as a conductive agent according to the weight ratio of 97.2:1.3:1.5, adding N-methylpyrrolidone (NMP), and stirring under the action of a vacuum stirrer until a mixed system becomes uniform and flowable anode slurry; uniformly coating the positive electrode slurry on an aluminum foil with the thickness of 9-12 mu m; baking the coated aluminum foil in 5 sections of baking ovens with different temperature gradients, drying the aluminum foil in a baking oven at 120 ℃ for 8 hours, and rolling and cutting to obtain the required positive plate.
(2) Preparation of negative plate
Preparing a slurry from an artificial graphite negative electrode material with the mass ratio of 96.5%, a single-walled carbon nanotube (SWCNT) conductive agent with the mass ratio of 0.1%, a conductive carbon black (SP) conductive agent with the mass ratio of 1%, a sodium carboxymethylcellulose (CMC) binder with the mass ratio of 1% and a Styrene Butadiene Rubber (SBR) binder with the mass ratio of 1.4% by a wet process, coating the slurry on the surface of a negative current collector copper foil, drying (the temperature is 85 ℃, the time is 5 hours), rolling and die cutting to obtain a negative electrode sheet.
(3) Preparation of non-aqueous electrolyte
In a glove box filled with argon (moisture)<10ppm, oxygen content<1ppm) ofEthylene Carbonate (EC), Propylene Carbonate (PC) and Propyl Propionate (PP) were mixed uniformly in a mass ratio of 1:1:2, and 14 wt.% of LiPF based on the total mass of the nonaqueous electrolyte was slowly added to the mixed solution6And 10-50 wt.% of ethyl propionate (the specific using amount of ethyl propionate is shown in table 1) and additives (the specific using amount and selection of additives are shown in table 1) based on the total mass of the nonaqueous electrolyte, and uniformly stirring to obtain the nonaqueous electrolyte.
(4) Preparation of the separator
The method comprises the steps of coating a ceramic layer with the thickness of 2 microns (the ceramic layer comprises 91 wt% of alumina, 4.5 wt% of polymethyl methacrylate and 4.5 wt% of sodium carboxymethyl cellulose) on the first surface of a polyethylene substrate with the thickness of 5 microns, coating glue layers with the thickness of 1 micron on the second surface of the polyethylene substrate and the surface of the ceramic layer respectively, wherein the glue layers are all non-full-coverage coating, namely the glue layers comprise glue coating areas and non-glue coating areas, the glue coating areas and the non-glue coating areas are arranged adjacently, glue is coated in the glue coating areas, glue is not coated in the non-glue coating areas, and the glue is polyvinylidene fluoride-hexafluoropropylene copolymer. The width of the glue coating area is 1 mm-5 mm, and the width of the non-glue coating area is 0.5 mm-2 mm (the specific width is shown in table 1).
(5) Preparation of lithium ion battery
Winding the prepared positive plate, the diaphragm and the prepared negative plate to obtain a naked battery cell without liquid injection; placing the bare cell in an outer packaging foil, injecting the prepared electrolyte into the dried bare cell, and performing vacuum packaging, standing, formation, shaping, sorting and other processes to obtain the required lithium ion battery.
TABLE 1 lithium ion batteries prepared in comparative examples 1 to 5 and examples 1 to 8
Figure BDA0003104241080000091
In the table: a is 4-methyl-1, 2-oxathiolane-2, 2-dioxide; b is tri (2-cyanoethyl) borate; c is trimethylsilyl substituted methylsulfonamide compound; specifically, D is a substance represented by formula 1-1; e is a substance represented by formula 1-2; the full-coating diaphragm refers to the coating glue which is coated in the coating layer.
Figure BDA0003104241080000092
The cells obtained in the above comparative examples and examples were subjected to electrochemical performance tests, as described below:
45 ℃ cycling experiment: placing the batteries obtained in the above examples and comparative examples in an environment of (45 +/-2) DEG C, standing for 2-3 hours, when the battery body reaches (45 +/-2) DEG C, keeping the cut-off current of the battery at 0.05C according to 1C constant current charging, standing for 5min after the battery is fully charged, then discharging to the cut-off voltage of 3.0V at 0.7C constant current, recording the highest discharge capacity of the previous 3 cycles as an initial capacity Q, and when the cycles reach 400 times, recording the last discharge capacity Q of the battery1The results are reported in Table 2.
The calculation formula used therein is as follows: capacity retention (%) ═ Q1/Q×100％。
Thermal shock test at 130 ℃: the batteries obtained in the above examples and comparative examples were heated at an initial temperature of 25. + -. 3 ℃ by convection or a circulating hot air oven at a temperature change rate of 5. + -. 2 ℃/min, heated to 130. + -. 2 ℃ and held for 60min, and the test was terminated, and the results of the battery state were recorded as shown in Table 2.
Low-temperature discharge experiment: discharging the batteries obtained in the above examples and comparative examples to 3.0V at ambient temperature of 25 + -3 deg.C at 0.2C, and standing for 5 min; charging at 0.7C, changing to constant voltage charging when the voltage at the cell terminal reaches the charging limit voltage, stopping charging until the charging current is less than or equal to the cut-off current, standing for 5 minutes, discharging to 3.0V at 0.2C, and recording the discharge capacity as the normal temperature capacity Q2. Then the battery cell is charged at 0.7C, when the voltage of the battery cell terminal reaches the charging limiting voltage, constant voltage charging is changed, and charging is stopped until the charging current is less than or equal to the cut-off current; standing the fully charged battery at-10 +/-2 ℃ for 4h, discharging to cut-off voltage of 3.0V at 0.3C, and recording discharge capacity Q3The low-temperature discharge capacity retention rate was calculated and reported in table 2.
The calculation formula used therein is as follows: low-temperature discharge capacity retention (%) ═ Q3/Q2×100％。
TABLE 2 experimental test results of the batteries obtained in comparative examples 1 to 5 and examples 1 to 8
Figure BDA0003104241080000101
As can be seen from the results of table 2: the comparative example and the example show that the safety performance of the lithium ion battery can be obviously improved by adding the optimized combination of the additive 4-methyl-1, 2-oxathiolane-2, 2-dioxide, the tri (2-cyanoethyl) borate, the trimethylsilyl substituted methylsulfonamide compound and the ethyl propionate solvent matched with the non-full-coverage coating adhesive diaphragm into the electrolyte, and the lithium ion battery has good low-temperature discharge performance.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. 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 lithium ion battery comprises a positive plate, a negative plate, a diaphragm arranged between the positive plate and the negative plate, and a non-aqueous electrolyte;
the diaphragm comprises a substrate, a ceramic layer, a first glue coating layer and a second glue coating layer, wherein the ceramic layer is coated on a first surface of the substrate, the first glue coating layer is coated on a second surface of the substrate, which is opposite to the first surface, and the second glue coating layer is coated on the surface of the ceramic layer;
the nonaqueous electrolyte comprises a nonaqueous organic solvent, an additive and a lithium salt, wherein the nonaqueous organic solvent comprises ethyl propionate; the additive comprises 4-methyl-1, 2-oxathiolane-2, 2-dioxide, tri (2-cyanoethyl) borate and at least one trimethylsilyl substituted methanesulfonamide compound shown as formula 1;
Figure FDA0003104241070000011
in formula 1, R is selected from aryl or
Figure FDA0003104241070000012
n is an integer between 1 and 6, and is a connecting point.
2. The lithium ion battery according to claim 1, wherein the trimethylsilyl-substituted methanesulfonamide compound represented by formula 1 is at least one selected from the following formulae 1-1 and 1-2:
Figure FDA0003104241070000013
3. the lithium ion battery according to claim 1 or 2, wherein the 4-methyl-1, 2-oxathiolane-2, 2-dioxide is added in an amount of 1 to 3 wt.% based on the total mass of the nonaqueous electrolytic solution; and/or the addition amount of the tris (2-cyanoethyl) borate is 0.5-3.5 wt% of the total mass of the nonaqueous electrolyte; and/or the trimethylsilyl-substituted methanesulfonamide compound represented by formula 1 is added in an amount of 0.2 to 1.8 wt.% based on the total mass of the nonaqueous electrolyte solution.
4. The lithium ion battery according to any one of claims 1 to 3, wherein the ethyl propionate is added in an amount of 10 to 50 wt.% of the total mass of the nonaqueous electrolyte solution.
5. The lithium ion battery of any of claims 1-4, wherein the ceramic layer comprises a ceramic, a binder, and a thickener; and/or the ceramic layer comprises the following components in percentage by mass: 85-97 wt% of ceramic, 1-10 wt% of binder and 0.5-10 wt% of thickener.
6. The lithium ion battery of any one of claims 1-5, wherein the first glue layer comprises a plurality of first glue areas and first non-glue areas which are arranged adjacent to each other, the first glue areas are coated with first glue, and the first non-glue areas are not coated with first glue; and/or the second glue coating layer comprises a plurality of second glue coating areas and second non-glue coating areas which are arranged adjacent to each other, the second glue coating areas are coated with second glue, and the second non-glue coating areas are not coated with the second glue.
7. The lithium ion battery of any one of claims 1-6, wherein the first glue layer is non-full-coverage coated, i.e. a first glue area and a first non-glue area are arranged adjacent to each other, the width of the first glue area is 1 mm-5 mm, and the width of the first non-glue area is 0.5 mm-2 mm; and/or the second glue coating layer is in non-full-coverage coating, namely a second glue coating area and a second non-glue coating area are arranged adjacent to each other, the width of the second glue coating area is 1-5 mm, and the width of the second non-glue coating area is 0.5-2 mm.
8. The lithium ion battery according to any one of claims 1 to 7, wherein the ceramic layer has a thickness of 1 to 5 μm; and/or the thickness of the first gluing layer is 0.5-2 μm; and/or the thickness of the second gluing layer is 0.5-2 μm.
9. The lithium ion battery according to any one of claims 1 to 8, wherein the positive electrode sheet comprises a positive electrode current collector and a positive electrode active material layer coated on one or both surfaces of the positive electrode current collector, the positive electrode active material layer comprising a positive electrode active material, a conductive agent and a binder,
the positive active material is selected from lithium cobaltate or lithium cobaltate subjected to doping coating treatment of two or more elements of Al, Mg, Mn, Cr, Ti and Zr, and the chemical formula of the lithium cobaltate subjected to doping coating treatment of two or more elements of Al, Mg, Mn, Cr, Ti and Zr is LixCo1-y1-y2-y3-y4Ay1By2Cy3Dy4O2；0.95≤x≤1.05，0.01≤y1≤0.1Y2 is more than or equal to 0.01 and less than or equal to 0.1, y3 is more than or equal to 0 and less than or equal to 0.1, y4 is more than or equal to 0 and less than or equal to 0.1, and A, B, C, D is selected from two or more elements of Al, Mg, Mn, Cr, Ti and Zr.
10. The lithium ion battery according to any one of claims 1 to 9, wherein the negative electrode sheet comprises a negative electrode current collector and a negative electrode active material layer coated on one or both surfaces of the negative electrode current collector, the negative electrode active material layer comprising a negative electrode active material, a conductive agent and a binder,
the negative active material is selected from graphite or a graphite composite material containing 1-12 wt% of SiOx/C or Si/C.
CN202110632599.0A 2021-06-07 2021-06-07 Lithium ion battery Pending CN113410510A (en)

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