WO2022257859A1 - Lithium-ion battery - Google Patents

Lithium-ion battery Download PDF

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Publication number
WO2022257859A1
WO2022257859A1 PCT/CN2022/096946 CN2022096946W WO2022257859A1 WO 2022257859 A1 WO2022257859 A1 WO 2022257859A1 CN 2022096946 W CN2022096946 W CN 2022096946W WO 2022257859 A1 WO2022257859 A1 WO 2022257859A1
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WIPO (PCT)
Prior art keywords
glue
coated
lithium
ion battery
battery according
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PCT/CN2022/096946
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French (fr)
Chinese (zh)
Inventor
母英迪
张祖来
王海
李素丽
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珠海冠宇电池股份有限公司
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Publication of WO2022257859A1 publication Critical 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

Definitions

  • the application belongs to the technical field of lithium-ion batteries, and in particular relates to a high-voltage lithium-ion battery with high safety performance.
  • lithium-ion batteries have been widely used in smartphones, tablet computers, smart wearables, power tools, and electric vehicles.
  • consumers' usage environment and demand for lithium-ion batteries continue to increase, which requires lithium-ion batteries to be able to take into account high and low temperature performance while having high safety.
  • the electrolyte is easy to decompose under high temperature and high voltage, and the electrolyte is easy to oxidize and decompose on the surface of the positive electrode to produce a large amount of gas, which leads to battery failure. Bulging and electrode interface damage, the safety performance of the battery is obviously deteriorated.
  • the purpose of this application is to provide a high-voltage lithium-ion battery with high safety performance in order to solve the problems of potential safety hazards in the use of the existing lithium-ion batteries, failure to balance the safety performance and electrochemical performance of the battery cell, and the like.
  • a lithium ion battery comprising a positive electrode sheet, a negative electrode sheet, a separator placed between the positive electrode sheet and the negative electrode sheet, and a non-aqueous electrolyte;
  • the diaphragm includes a base material, a ceramic layer, a first glue layer and a second glue layer, the ceramic layer is coated on the first surface of the base material, and the first glue layer is coated on the base material and the second glue layer. a second surface opposite to the first surface, the second glue layer is coated on the surface of the ceramic layer;
  • the non-aqueous electrolytic solution includes a non-aqueous organic solvent, an additive and a lithium salt, wherein the non-aqueous organic solvent includes ethyl propionate; the additive includes 4-methyl-1,2-oxathiolane- 2,2-dioxide, tris(2-cyanoethyl) borate and at least one trimethylsilyl-substituted methylsulfonamide compound represented by formula 1;
  • R is selected from aryl or n is an integer between 1 and 6, and * is a connection point.
  • R is selected from C 6-12 aryl (such as phenyl) or n is an integer between 1 and 3 (such as ), * is the connection point.
  • the CAS number of the 4-methyl-1,2-oxathiolane-2,2-dioxide is 15606-89-0; the tris(2-cyanoethyl)boron
  • the CAS number of the ester is 126755-67-7.
  • the additives can be prepared by methods known in the art, or purchased from commercial channels.
  • the trimethylsilyl-substituted methylsulfonamide compound represented by the formula 1 is selected from at least one of the following formula 1-1 and formula 1-2:
  • the added amount of the 4-methyl-1,2-oxathiolane-2,2-dioxide is 1-3wt.% of the total mass of the non-aqueous electrolyte, for example, 1wt. %, 1.2wt.%, 1.4wt.%, 1.5wt.%, 1.8wt.%, 2wt.%, 2.2wt.%, 2.5wt.%, 2.8wt.% or 3wt.%.
  • the added amount of the tris (2-cyanoethyl) borate is 0.5 to 3.5wt.% of the total mass of the non-aqueous electrolyte, for example 0.5wt.%, 0.6wt.%, 0.8wt. %, 0.9wt.%, 1wt.%, 1.2wt.%, 1.4wt.%, 1.5wt.%, 1.8wt.%, 2wt.%, 2.2wt.%, 2.5wt.%, 2.8wt.%, 3wt.%, 3.2wt.%, 3.4wt.%, or 3.5wt.%.
  • the addition amount of the trimethylsilyl-substituted methylsulfonamide compound represented by the formula 1 is 0.2-1.8wt.% of the total mass of the non-aqueous electrolyte, for example, 0.2wt.%, 0.3wt. .%, 0.4wt.%, 0.5wt.%, , 0.6wt.%, 0.8wt.%, 0.9wt.%, 1wt.%, 1.2wt.%, 1.3wt.%, 1.4wt.%, 1.5wt .%, 1.6wt.%, 1.7wt.%, or 1.8wt.%.
  • the amount of ethyl propionate added is 10-50wt.% of the total mass of the non-aqueous electrolyte, preferably 20-40wt.%, such as 10wt.%, 15wt.%, 20wt.%, 25wt. .%, 30wt.%, 35wt.%, 40wt.%, 45wt.% or 50wt.%.
  • the non-aqueous organic solvent further includes at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl propionate and propyl acetate.
  • the lithium salt is selected from at least one of lithium bistrifluoromethanesulfonimide, lithium bisfluorosulfonimide and lithium hexafluorophosphate, which accounts for 13-20wt.% of the total mass of the non-aqueous electrolyte .
  • the non-aqueous electrolyte also includes ethylene carbonate, 1,3-propane sultone, ethylene glycol bis(propionitrile) ether, 1,2,3-tris(2-cyanoethoxy base) propane, lithium bisoxalate borate and lithium difluorooxalate borate; it accounts for 0-10wt.% of the total mass of the non-aqueous electrolyte.
  • the substrate is selected from one or more of polyethylene, polypropylene, polyimide, polyamide and aramid.
  • the ceramic layer includes ceramic, binder and thickener.
  • the ceramic is selected from one or more of alumina, boehmite, magnesia and magnesium hydroxide.
  • the binder is selected from polytetrafluoroethylene, polyvinylidene fluoride, modified polyvinylidene fluoride-hexafluoropropylene and its copolymers, polyimide, polyacrylonitrile and polymethacrylate one or more of esters.
  • the thickener is selected from one or both of sodium carboxymethylcellulose and lithium carboxymethylcellulose.
  • the ceramic layer includes the following components in mass percentage: 85-97wt% of ceramics, 1-10wt% of binder and 0.5-10wt% of thickener.
  • the first glue-coated layer includes several first glue-coated areas and first non-glue-coated areas arranged adjacent to each other, the first glue-coated area is coated with the first glue, and the first glue-coated area is coated with the first glue-coated area.
  • the first glue is not coated in the non-glue area.
  • the first glue-coated layer includes a first glue-coated region, a first non-glue-coated region, a first glue-coated region, a first non-glue-coated region...the first glue-coated region, which are arranged adjacently in sequence.
  • the second gluing layer includes several second gluing areas and second non-gluing areas arranged adjacent to each other, the second gluing area is coated with second gluing, and the second gluing area is coated with second gluing.
  • the second glue is not applied in the non-glue area.
  • the second glue-coated layer includes a second glue-coated area, a second non-glue-coated area, a second glue-coated area, a second non-glue-coated area... a second glue-coated area arranged adjacently in sequence.
  • the first coating includes polytetrafluoroethylene, polyvinylidene fluoride, modified polyvinylidene fluoride-hexafluoropropylene and its copolymers, polyimide, polyacrylonitrile and polymethacrylate One or more of the esters.
  • the second coating includes polytetrafluoroethylene, polyvinylidene fluoride, modified polyvinylidene fluoride-hexafluoropropylene and its copolymers, polyimide, polyacrylonitrile and polymethacrylate One or more of the esters.
  • the first coating and the second coating are the same or different, preferably the same.
  • the first glue-coated layer is non-full-coverage coating, that is, the first glue-coated area and the first non-glue-coated area are arranged adjacent to each other, and the width of the first glue-coated area is 1 mm to 1 mm. 5mm, the width of the first non-glue-coated area is 0.5mm-2mm.
  • the second gluing layer is non-full-coverage coating, that is, the second gluing area and the second non-gluing area are arranged adjacent to each other, and the width of the second gluing area is 1 mm to 5mm, and the width of the second non-glue-coated area is 0.5mm-2mm.
  • the thickness of the substrate is 5-20 ⁇ m, such as 5 ⁇ m, 8 ⁇ m, 10 ⁇ m, 15 ⁇ m, 18 ⁇ m or 20 ⁇ m.
  • the thickness of the ceramic layer is 1-5 ⁇ m, such as 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m or 5 ⁇ m.
  • the thickness of the first glue layer is 0.5-2 ⁇ m, such as 0.5 ⁇ m, 0.8 ⁇ m, 1 ⁇ m, 1.2 ⁇ m, 1.5 ⁇ m, 1.8 ⁇ m or 2 ⁇ m.
  • the thickness of the second glue layer is 0.5-2 ⁇ m, such as 0.5 ⁇ m, 0.8 ⁇ m, 1 ⁇ m, 1.2 ⁇ m, 1.5 ⁇ m, 1.8 ⁇ m or 2 ⁇ m.
  • the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer coated on one or both sides of the positive electrode current collector, and the positive electrode active material layer includes a positive electrode active material, a conductive agent and a binder.
  • the negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer coated on one or both sides of the negative electrode current collector, and the negative electrode active material layer includes a negative electrode active material, a conductive agent and a binder.
  • the positive electrode active material is selected from lithium cobaltate or lithium cobaltate that has been doped and coated with two or more elements in Al, Mg, Mn, Cr, Ti, Zr.
  • the chemical formula of lithium cobaltate coated with two or more elements in Mg, Mn, Cr, Ti, Zr is Li x Co 1-y1-y2-y3-y4 A y1 B y2 C y3 D y4 O 2 ; Two or more elements in Zr.
  • the median particle size D50 of the lithium cobalt oxide coated with two or more elements in Al, Mg, Mn, Cr, Ti, Zr is 10-17 ⁇ m, and the specific surface area BET is 0.15 ⁇ 0.45 m 2 /g.
  • the negative electrode active material is selected from graphite or graphite composite material containing 1-12wt.% SiOx/C or Si/C, wherein 0 ⁇ x ⁇ 2.
  • the charging cut-off voltage of the lithium-ion battery is 4.45V or above.
  • the application provides a high-voltage lithium-ion battery with high safety performance.
  • the lithium ion battery prepared by combining the positive and negative electrode materials through the synergistic effect of the diaphragm and the electrolyte can effectively improve the safety performance of the battery core while taking into account the low temperature performance of the battery core.
  • the lithium-ion battery includes a non-aqueous electrolyte; the non-aqueous electrolyte includes a non-aqueous organic solvent, an additive and a lithium salt, and the synergistic effect of the additive and the solvent in the electrolyte formula makes the battery cell take into account high and low temperature performance, wherein three (2 -Cyanoethyl) borate and trimethylsilyl-substituted methylsulfonamide compounds shown in Formula 1 can jointly form a thicker and stable CEI protective film on the surface of the positive electrode, improving the performance of the positive electrode material under high temperature and high voltage.
  • a relatively high content of ethyl propionate is added to the non-aqueous electrolyte of the present application, which can reduce the viscosity of the solvent, improve the wettability and ion conductivity of the electrolyte, and improve the low-temperature performance of the battery cell.
  • ethyl propionate due to the addition of a large amount of ethyl propionate to the electrolyte, ethyl propionate has a low boiling point and strong activity. It is unstable in the cell and is easily decomposed by the redox of the active material, thereby releasing a large amount of heat from the reaction and causing the safety performance of the battery to fail.
  • a separator containing a non-full coverage coated adhesive layer is used, and a large number of channels are added between the positive electrode and the separator, the negative electrode and the separator inside the battery, and the heat and generated heat in the center of the battery cell can be removed when the battery is in a high temperature environment.
  • Figure 1 Schematic diagram of the cross-section of the separator in the lithium-ion battery of the present application.
  • the lithium-ion batteries of Comparative Examples 1-5 and Examples 1-8 were prepared according to the following preparation methods, the only difference being the choice of diaphragm and electrolyte, the specific differences are shown in Table 1.
  • a 1% sodium carboxymethylcellulose (CMC) binder and a 1.4% styrene-butadiene rubber (SBR) binder are made into a slurry by a wet process and coated on the negative electrode current collector copper foil The surface was dried (temperature: 85° C., time: 5 h), rolled and die-cut to obtain the negative electrode sheet.
  • the first surface of the polyethylene substrate with a thickness of 5 ⁇ m is coated with a ceramic layer with a thickness of 2 ⁇ m (the composition of the ceramic layer is: 91wt% aluminum oxide, 4.5wt% polymethyl methacrylate, 4.5wt% Sodium carboxymethyl cellulose), on the second surface of the polyethylene substrate and the surface of the ceramic layer, respectively coat a layer of glue coating with a thickness of 1 ⁇ m, and the glue coating is all non-full coverage coating, that is, the
  • the glue-coated layer includes a glue-coated area and a non-glue-coated area, and the glue-coated area and the non-glue-coated area are arranged adjacent to each other, the glue-coated area is coated with glue, and the non-glued area is not coated.
  • Overcoat glue said glue is polyvinylidene fluoride-hexafluoropropylene copolymer.
  • the width of the glue-coated area is 1mm-5mm, and the width of the non-glue-coated area is 0.5mm-2mm (the specific width is shown in Table 1).
  • A is 4-methyl-1,2-oxathiolane-2,2-dioxide; B is tris(2-cyanoethyl) borate; C is trimethylsilyl Substituted methylsulfonamide compounds; specifically, D is the substance shown in formula 1-1; E is the substance shown in formula 1-2; fully coated separator means that the coating is completely coated with glue.
  • Electrochemical performance test is carried out to the battery obtained in the above-mentioned comparative examples and examples, and the relevant instructions are as follows:
  • 130°C thermal shock test Heat the batteries obtained in the above examples and comparative examples with a convection method or a circulating hot air box at an initial temperature of 25 ⁇ 3°C, with a temperature change rate of 5 ⁇ 2°C/min, and then heat up to 130 ⁇ 2°C , keep the test for 60 minutes and end the test, record the battery status results as shown in Table 2.

Abstract

The present application provides a lithium-ion battery. According to the present application, the lithium-on battery prepared by means of the synergistic effect of a separator and an electrolyte and the combination of positive and negative electrode materials can achieve the low temperature performance of a battery cell while effectively improving the safety performance of the battery cell. 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 formulation enables the battery cell to achieve both high and low temperature performance. Tris(2-cyanoethyl)borate and the trimethylsilyl-substituted methylsulfonamide compound represented by formula 1 can jointly form a thick and stable CEI protective film on the surface of a positive electrode, thereby improving the stability of the positive electrode material at high temperature and high voltage, preventing the electrolyte from being oxidized on the surface of the positive electrode, and reducing the exotherm of a side reaction.

Description

一种锂离子电池A lithium ion battery
本申请要求于2021年06月07日提交中国专利局、申请号为202110632599.0、申请名称为“一种锂离子电池”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application with the application number 202110632599.0 and the application title "A Lithium-ion Battery" submitted to the China Patent Office on June 7, 2021, the entire contents of which are incorporated in this application by reference.
技术领域technical field
本申请属于锂离子电池技术领域，具体涉及一种具有高安全性能的高电压锂离子电池。The application belongs to the technical field of lithium-ion batteries, and in particular relates to a high-voltage lithium-ion battery with high safety performance.
背景技术Background technique
近年来，锂离子电池在智能手机、平板电脑、智能穿戴、电动工具和电动汽车等领域得到了广泛的应用。随着锂离子电池的广泛应用，消费者对锂离子电池的使用环境、需求不断提高，这就要求锂离子电池能够兼顾高低温性能的同时具有高安全性。In recent years, lithium-ion batteries have been widely used in smartphones, tablet computers, smart wearables, power tools, and electric vehicles. With the wide application of lithium-ion batteries, consumers' usage environment and demand for lithium-ion batteries continue to increase, which requires lithium-ion batteries to be able to take into account high and low temperature performance while having high safety.
目前，锂离子电池在使用过程中存在安全隐患，例如当电池处于持续高温等一些极端的使用情况下容易发生严重的安全事故，起火甚至爆炸。造成这些问题的主要原因一方面是正极材料在高温高电压下结构不稳定，金属离子极易从正极中溶出并在负极表面还原沉积，从而破坏负极SEI膜的结构，导致负极阻抗和电池厚度不断增大，导致电芯温度持续上升，热量不断积蓄无法释放引起安全事故；另一方面是电解液在高温高电压下易分解，电解液容易在正极表面发生氧化分解产生大量的气体，从而导致电池鼓胀和电极界面破坏，电池安全性能明显变差。At present, there are potential safety hazards in the use of lithium-ion batteries. For example, when the battery is in extreme conditions such as continuous high temperature, serious safety accidents, fires or even explosions are prone to occur. The main reason for these problems is that the structure of the positive electrode material is unstable under high temperature and high voltage, and metal ions are easily dissolved from the positive electrode and deposited on the surface of the negative electrode, thereby destroying the structure of the SEI film of the negative electrode, resulting in constant negative electrode impedance and battery thickness. increase, resulting in the continuous rise of the battery temperature, and the continuous accumulation of heat that cannot be released, causing safety accidents; on the other hand, the electrolyte is easy to decompose under high temperature and high voltage, and the electrolyte is easy to oxidize and decompose on the surface of the positive electrode to produce a large amount of gas, which leads to battery failure. Bulging and electrode interface damage, the safety performance of the battery is obviously deteriorated.
基于此现状，急需开发具有高安全性的高电压锂离子电池，例如通过向电解液中添加阻燃剂(如磷酸三甲酯等)能够改善安全性能，但这些添加剂的使用往往会导致电池性能严重劣化。因此能够开发在不影响电池电化学性能的前提下，同时具有高安全性的高电压锂离子电池是目前的首要任务。Based on this status quo, there is an urgent need to develop high-voltage lithium-ion batteries with high safety. For example, the safety performance can be improved by adding flame retardants (such as trimethyl phosphate, etc.) to the electrolyte, but the use of these additives often leads to battery performance. Severely deteriorated. Therefore, it is a top priority to develop high-voltage lithium-ion batteries with high safety without affecting the electrochemical performance of the battery.
发明内容Contents of the invention
本申请的目的是为了解决现有的锂离子电池在使用过程中存在安全隐患、电芯安全性能与电化学性能未能兼顾等问题，提供一种具有高安全性能的高电压锂离子电池。The purpose of this application is to provide a high-voltage lithium-ion battery with high safety performance in order to solve the problems of potential safety hazards in the use of the existing lithium-ion batteries, failure to balance the safety performance and electrochemical performance of the battery cell, and the like.
为实现上述目的，本申请采用如下的技术方案：In order to achieve the above object, the application adopts the following technical solutions:
一种锂离子电池，其包括正极片、负极片、置于正极片和负极片之间的隔膜，以及非水电解液；A lithium ion battery comprising a positive electrode sheet, a negative electrode sheet, a separator placed between the positive electrode sheet and the negative electrode sheet, and a non-aqueous electrolyte;
所述隔膜包括基材、陶瓷层、第一涂胶层和第二涂胶层，所述陶瓷层涂覆在基材的第一表面，所述第一涂胶层涂覆在基材的与第一表面相对的第二表面，所述第二涂胶层涂覆在陶瓷层表面；The diaphragm includes a base material, a ceramic layer, a first glue layer and a second glue layer, the ceramic layer is coated on the first surface of the base material, and the first glue layer is coated on the base material and the second glue layer. a second surface opposite to the first surface, the second glue layer is coated on the surface of the ceramic layer;
所述非水电解液包括非水有机溶剂、添加剂和锂盐，其中所述非水有机溶剂包括丙酸乙酯；所述添加剂包括4-甲基-1,2-氧硫杂环戊烷-2,2-二氧化物、三(2-氰乙基)硼酸酯和至少一种式1所示的三甲基硅基取代甲基磺酰胺类化合物；The non-aqueous electrolytic solution includes a non-aqueous organic solvent, an additive and a lithium salt, wherein the non-aqueous organic solvent includes ethyl propionate; the additive includes 4-methyl-1,2-oxathiolane- 2,2-dioxide, tris(2-cyanoethyl) borate and at least one trimethylsilyl-substituted methylsulfonamide compound represented by formula 1;
Figure PCTCN2022096946-appb-000001
Figure PCTCN2022096946-appb-000001
式1中，R选自芳基或
Figure PCTCN2022096946-appb-000002
n为1～6之间的整数，*为连接点。 In formula 1, R is selected from aryl or
Figure PCTCN2022096946-appb-000002
n is an integer between 1 and 6, and * is a connection point.
根据本申请，R选自C 6-12芳基(如苯基)或n为1～3之间的整数(如
Figure PCTCN2022096946-appb-000003
)，*为连接点。 According to the present application, R is selected from C 6-12 aryl (such as phenyl) or n is an integer between 1 and 3 (such as
Figure PCTCN2022096946-appb-000003
), * is the connection point.
根据本申请，所述4-甲基-1,2-氧硫杂环戊烷-2,2-二氧化物的CAS号为15606-89-0；所述三(2-氰乙基)硼酸酯的CAS号为126755-67-7。According to the present application, the CAS number of the 4-methyl-1,2-oxathiolane-2,2-dioxide is 15606-89-0; the tris(2-cyanoethyl)boron The CAS number of the ester is 126755-67-7.
根据本申请，所述添加剂均可以采用本领域已知的方法制备得到，也可以采用商业途径购买后获得。According to the present application, the additives can be prepared by methods known in the art, or purchased from commercial channels.
根据本申请，所述式1所示的三甲基硅基取代甲基磺酰胺类化合物选自如下式1-1和式1-2中的至少一种：According to the present application, the trimethylsilyl-substituted methylsulfonamide compound represented by the formula 1 is selected from at least one of the following formula 1-1 and formula 1-2:
Figure PCTCN2022096946-appb-000004
Figure PCTCN2022096946-appb-000004
根据本申请，所述4-甲基-1,2-氧硫杂环戊烷-2,2-二氧化物的添加量为非水电解液总质量的1～3wt.％，例如为1wt.％、1.2wt.％、1.4wt.％、1.5wt.％、1.8wt.％、2wt.％、2.2wt.％、2.5wt.％、2.8wt.％或3wt.％。According to the present application, the added amount of the 4-methyl-1,2-oxathiolane-2,2-dioxide is 1-3wt.% of the total mass of the non-aqueous electrolyte, for example, 1wt. %, 1.2wt.%, 1.4wt.%, 1.5wt.%, 1.8wt.%, 2wt.%, 2.2wt.%, 2.5wt.%, 2.8wt.% or 3wt.%.
根据本申请，所述三(2-氰乙基)硼酸酯的添加量为非水电解液总质量的0.5～3.5wt.％，例如为0.5wt.％、0.6wt.％、0.8wt.％、0.9wt.％、1wt.％、1.2wt.％、1.4wt.％、1.5wt.％、1.8wt.％、2wt.％、2.2wt.％、2.5wt.％、2.8wt.％、3wt.％、3.2wt.％、3.4wt.％或3.5wt.％。According to the present application, the added amount of the tris (2-cyanoethyl) borate is 0.5 to 3.5wt.% of the total mass of the non-aqueous electrolyte, for example 0.5wt.%, 0.6wt.%, 0.8wt. %, 0.9wt.%, 1wt.%, 1.2wt.%, 1.4wt.%, 1.5wt.%, 1.8wt.%, 2wt.%, 2.2wt.%, 2.5wt.%, 2.8wt.%, 3wt.%, 3.2wt.%, 3.4wt.%, or 3.5wt.%.
根据本申请，所述式1所示的三甲基硅基取代甲基磺酰胺类化合物的添加量为非水电解液总质量的0.2～1.8wt.％，例如为0.2wt.％、0.3wt.％、0.4wt.％、0.5wt.％、、0.6wt.％、0.8wt.％、0.9wt.％、1wt.％、1.2wt.％、1.3wt.％、1.4wt.％、1.5wt.％、1.6wt.％、1.7wt.％或1.8wt.％。According to the present application, the addition amount of the trimethylsilyl-substituted methylsulfonamide compound represented by the formula 1 is 0.2-1.8wt.% of the total mass of the non-aqueous electrolyte, for example, 0.2wt.%, 0.3wt. .%, 0.4wt.%, 0.5wt.%, , 0.6wt.%, 0.8wt.%, 0.9wt.%, 1wt.%, 1.2wt.%, 1.3wt.%, 1.4wt.%, 1.5wt .%, 1.6wt.%, 1.7wt.%, or 1.8wt.%.
根据本申请，所述丙酸乙酯的添加量为非水电解液总质量的10～50wt.％，优选地20～40wt.％，例如为10wt.％、15wt.％、20wt.％、25wt.％、30wt.％、35wt.％、40wt.％、45wt.％或50wt.％。According to the present application, the amount of ethyl propionate added is 10-50wt.% of the total mass of the non-aqueous electrolyte, preferably 20-40wt.%, such as 10wt.%, 15wt.%, 20wt.%, 25wt. .%, 30wt.%, 35wt.%, 40wt.%, 45wt.% or 50wt.%.
根据本申请，所述的非水有机溶剂还包括碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、丙酸丙酯和乙酸丙酯中的至少一种。According to the present application, the non-aqueous organic solvent further includes at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl propionate and propyl acetate.
根据本申请，所述锂盐选自双三氟甲基磺酰亚胺锂、双氟磺酰亚胺锂和六氟磷酸锂中的至少一种，其占非水电解液总质量的13～20wt.％。According to the present application, the lithium salt is selected from at least one of lithium bistrifluoromethanesulfonimide, lithium bisfluorosulfonimide and lithium hexafluorophosphate, which accounts for 13-20wt.% of the total mass of the non-aqueous electrolyte .
根据本申请，所述非水电解液还包括碳酸亚乙酯、1,3-丙磺酸内酯、乙二醇双(丙腈)醚、1,2,3-三(2-氰乙氧基)丙烷、双草酸硼酸锂和二氟草酸硼酸锂中的至少一种；其占非水电解液总质量的0～10wt.％。According to the present application, the non-aqueous electrolyte also includes ethylene carbonate, 1,3-propane sultone, ethylene glycol bis(propionitrile) ether, 1,2,3-tris(2-cyanoethoxy base) propane, lithium bisoxalate borate and lithium difluorooxalate borate; it accounts for 0-10wt.% of the total mass of the non-aqueous electrolyte.
根据本申请，所述基材选自聚乙烯、聚丙烯、聚酰亚胺、聚酰胺和芳纶中的一种或多种。According to the present application, the substrate is selected from one or more of polyethylene, polypropylene, polyimide, polyamide and aramid.
根据本申请，所述陶瓷层包括陶瓷、粘结剂和增稠剂。According to the present application, the ceramic layer includes ceramic, binder and thickener.
根据本申请，所述陶瓷选自氧化铝、勃姆石、氧化镁和氢氧化镁中的一种或多种。According to the present application, the ceramic is selected from one or more of alumina, boehmite, magnesia and magnesium hydroxide.
根据本申请，所述粘结剂选自聚四氟乙烯、聚偏氟乙烯、聚偏氟乙烯-六氟丙烯改性及其共聚物、聚酰亚胺、聚丙烯腈和聚甲基丙烯酸甲酯中的一种或多种。According to the present application, the binder is selected from polytetrafluoroethylene, polyvinylidene fluoride, modified polyvinylidene fluoride-hexafluoropropylene and its copolymers, polyimide, polyacrylonitrile and polymethacrylate one or more of esters.
根据本申请，所述增稠剂选自羧甲基纤维素钠、羧甲基纤维素锂中的一种或两种。According to the present application, the thickener is selected from one or both of sodium carboxymethylcellulose and lithium carboxymethylcellulose.
根据本申请，所述陶瓷层包括如下质量百分含量的各组分：85～97wt％的陶瓷、1～10wt％的粘结剂和0.5～10wt％的增稠剂。According to the present application, the ceramic layer includes the following components in mass percentage: 85-97wt% of ceramics, 1-10wt% of binder and 0.5-10wt% of thickener.
根据本申请，所述第一涂胶层包括若干彼此相邻设置的第一涂胶区和第一非涂胶区，所述第一涂胶区内涂覆第一涂胶，所述第一非涂胶区内不涂覆第一涂胶。示例性地，所述第一涂胶层包括依次相邻设置的第一涂胶区、第一非涂胶区、第一涂胶区、第一非涂胶区……第一涂胶区。According to the present application, the first glue-coated layer includes several first glue-coated areas and first non-glue-coated areas arranged adjacent to each other, the first glue-coated area is coated with the first glue, and the first glue-coated area is coated with the first glue-coated area. The first glue is not coated in the non-glue area. Exemplarily, the first glue-coated layer includes a first glue-coated region, a first non-glue-coated region, a first glue-coated region, a first non-glue-coated region...the first glue-coated region, which are arranged adjacently in sequence.
根据本申请，所述第二涂胶层包括若干彼此相邻设置的第二涂胶区和第二非涂胶区，所述第二涂胶区内涂覆第二涂胶，所述第二非涂胶区内不涂覆第二涂胶。示例性地，所述第二涂胶层包括依次相邻设置的第二涂胶区、第二非涂胶区、第二涂胶区、第二非涂胶区……第二涂胶区。According to the present application, the second gluing layer includes several second gluing areas and second non-gluing areas arranged adjacent to each other, the second gluing area is coated with second gluing, and the second gluing area is coated with second gluing. The second glue is not applied in the non-glue area. Exemplarily, the second glue-coated layer includes a second glue-coated area, a second non-glue-coated area, a second glue-coated area, a second non-glue-coated area... a second glue-coated area arranged adjacently in sequence.
根据本申请，所述第一涂胶包括聚四氟乙烯、聚偏氟乙烯、聚偏氟乙烯-六氟丙烯改性及其共聚物、聚酰亚胺、聚丙烯腈和聚甲基丙烯酸甲酯中的一种或几种。According to the present application, the first coating includes polytetrafluoroethylene, polyvinylidene fluoride, modified polyvinylidene fluoride-hexafluoropropylene and its copolymers, polyimide, polyacrylonitrile and polymethacrylate One or more of the esters.
根据本申请，所述第二涂胶包括聚四氟乙烯、聚偏氟乙烯、聚偏氟乙烯-六氟丙烯改性及其共聚物、聚酰亚胺、聚丙烯腈和聚甲基丙烯酸甲酯中的一种或几种。According to the present application, the second coating includes polytetrafluoroethylene, polyvinylidene fluoride, modified polyvinylidene fluoride-hexafluoropropylene and its copolymers, polyimide, polyacrylonitrile and polymethacrylate One or more of the esters.
根据本申请，所述第一涂胶和所述第二涂胶相同或不同，优选为相同。According to the present application, the first coating and the second coating are the same or different, preferably the same.
根据本申请，所述第一涂胶层为非全覆盖涂覆，即第一涂胶区和第一非涂胶区彼此相邻设置，且所述第一涂胶区的幅宽为1mm～5mm，所述第一非涂胶区的幅宽为0.5mm～2mm。According to the present application, the first glue-coated layer is non-full-coverage coating, that is, the first glue-coated area and the first non-glue-coated area are arranged adjacent to each other, and the width of the first glue-coated area is 1 mm to 1 mm. 5mm, the width of the first non-glue-coated area is 0.5mm-2mm.
根据本申请，所述第二涂胶层为非全覆盖涂覆，即第二涂胶区和第二非涂胶区彼此相邻设置，且所述第二涂胶区的幅宽为1mm～5mm，所述第二非涂胶区的幅宽为0.5mm～2mm。According to the present application, the second gluing layer is non-full-coverage coating, that is, the second gluing area and the second non-gluing area are arranged adjacent to each other, and the width of the second gluing area is 1 mm to 5mm, and the width of the second non-glue-coated area is 0.5mm-2mm.
根据本申请，所述基材的厚度为5～20μm，例如为5μm、8μm、10μm、15μm、18μm或20μm。According to the present application, the thickness of the substrate is 5-20 μm, such as 5 μm, 8 μm, 10 μm, 15 μm, 18 μm or 20 μm.
根据本申请，所述陶瓷层的厚度为1～5μm，例如为1μm、2μm、3μm、4μm或5μm。According to the present application, the thickness of the ceramic layer is 1-5 μm, such as 1 μm, 2 μm, 3 μm, 4 μm or 5 μm.
根据本申请，所述第一涂胶层的厚度为0.5～2μm，例如为0.5μm、0.8μm、1μm、1.2μm、1.5μm、1.8μm或2μm。According to the present application, 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.
根据本申请，所述第二涂胶层的厚度为0.5～2μm，例如为0.5μm、0.8μm、1μm、1.2μm、1.5μm、1.8μm或2μm。According to the present application, the thickness of the second 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.
根据本申请，所述正极片包括正极集流体和涂覆在正极集流体一侧或两侧表面的正极活性物质层，所述正极活性物质层包括正极活性物质、导电剂和粘结剂。According to the present application, the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer coated on one or both sides of the positive electrode current collector, and the positive electrode active material layer includes a positive electrode active material, a conductive agent and a binder.
根据本申请，所述负极片包括负极集流体和涂覆在负极集流体一侧或两侧表面的负极活性物质层，所述负极活性物质层包括负极活性物质、导电剂和粘结剂。According to the present application, the negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer coated on one or both sides of the negative electrode current collector, and the negative electrode active material layer includes a negative electrode active material, a conductive agent and a binder.
根据本申请，所述的正极活性物质选自钴酸锂或经过Al、Mg、Mn、Cr、Ti、Zr中两种或多种元素掺杂包覆处理的钴酸锂，所述经过Al、Mg、Mn、Cr、Ti、Zr中两种或多种元素掺杂包覆处理的钴酸锂的化学式为Li xCo 1-y1-y2-y3-y4A y1B y2C y3D y4O 2；0.95≤x≤1.05，0.01≤y1≤0.1，0.01≤y2≤0.1，0≤y3≤0.1，0≤y4≤0.1，A、B、C、D选自Al、Mg、Mn、Cr、Ti、Zr中两种或多种元素。 According to the present application, the positive electrode active material is selected from lithium cobaltate or lithium cobaltate that has been doped and coated with two or more elements in Al, Mg, Mn, Cr, Ti, Zr. The chemical formula of lithium cobaltate coated with two or more elements in Mg, Mn, Cr, Ti, Zr is Li x Co 1-y1-y2-y3-y4 A y1 B y2 C y3 D y4 O 2 ; Two or more elements in Zr.
根据本申请，所述经过Al、Mg、Mn、Cr、Ti、Zr中两种或多种元素掺杂包覆处理的钴酸锂的中值粒径D50为10～17μm，比表面积BET为0.15～0.45m 2/g。 According to the present application, the median particle size D50 of the lithium cobalt oxide coated with two or more elements in Al, Mg, Mn, Cr, Ti, Zr is 10-17 μm, and the specific surface area BET is 0.15 ~0.45 m 2 /g.
根据本申请，所述的负极活性物质选自石墨或含1～12wt.％SiOx/C或Si/C的石墨复合材料，其中0<x<2。According to the present application, the negative electrode active material is selected from graphite or graphite composite material containing 1-12wt.% SiOx/C or Si/C, wherein 0<x<2.
根据本申请，所述锂离子电池的充电截止电压在4.45V及以上。According to the present application, the charging cut-off voltage of the lithium-ion battery is 4.45V or above.
本申请的有益效果在于：The beneficial effect of this application is:
本申请提供一种具有高安全性能的高电压锂离子电池。The application provides a high-voltage lithium-ion battery with high safety performance.
本申请通过隔膜与电解液的协同作用在正负极材料组合下联用后制备得到的锂离子电池能够有效提高电芯安全性能的同时兼顾电芯低温性能。In this application, the lithium ion battery prepared by combining the positive and negative electrode materials through the synergistic effect of the diaphragm and the electrolyte can effectively improve the safety performance of the battery core while taking into account the low temperature performance of the battery core.
所述锂离子电池包括非水电解液；所述非水电解液包括非水有机溶剂、添加剂和锂盐，电解液配方中添加剂与溶剂的协同作用使电芯兼顾高低温性能，其中三(2-氰乙基)硼酸酯和式1所示的三甲基硅基取代甲基磺酰胺类化合物能够在正极表面联合形成较厚且稳定的CEI保护膜，提高正极材料在高温高电压下的稳定性，阻止电解液在正极表面被氧化，降低副反应放热；同时4-甲基-1,2-氧硫杂环戊烷-2,2-二氧化物和式1所示的三甲基硅基取代甲基磺酰胺类化合物可在负极表面形成一层十分坚固但阻抗较大的SEI膜，强有力的阻止电解液在负极表面被还原，阻止电池自放电提高电芯耐高温特性。同时，本申请的非水电解液中还加入了较高含量的丙酸乙酯，其可以降低溶剂粘度，提高电解液浸润性以及离子电导率，提高电芯低温性能。The lithium-ion battery includes a non-aqueous electrolyte; the non-aqueous electrolyte includes a non-aqueous organic solvent, an additive and a lithium salt, and the synergistic effect of the additive and the solvent in the electrolyte formula makes the battery cell take into account high and low temperature performance, wherein three (2 -Cyanoethyl) borate and trimethylsilyl-substituted methylsulfonamide compounds shown in Formula 1 can jointly form a thicker and stable CEI protective film on the surface of the positive electrode, improving the performance of the positive electrode material under high temperature and high voltage. Stability, preventing the electrolyte from being oxidized on the surface of the positive electrode, reducing the heat generation of side reactions; while 4-methyl-1,2-oxathiolane-2,2-dioxide and trimethyl Silicon-based substituted methylsulfonamide compounds can form a very strong but high-resistance SEI film on the surface of the negative electrode, which can effectively prevent the electrolyte from being reduced on the surface of the negative electrode, prevent the battery from self-discharging and improve the high temperature resistance of the battery. At the same time, a relatively high content of ethyl propionate is added to the non-aqueous electrolyte of the present application, which can reduce the viscosity of the solvent, improve the wettability and ion conductivity of the electrolyte, and improve the low-temperature performance of the battery cell.
但是，由于电解液中加入了大量了丙酸乙酯，丙酸乙酯沸点较低且活性较强在电芯内不稳定易于被活性物质氧化还原分解，从而反应放出大量热引发电池安全性能失效，本申请中采用含有非全覆盖涂覆的涂胶层的隔膜，在电池内部正极与隔膜、负极与隔膜之间增加大量的通道，在电池处于高温环境下可以排除电芯中心的热量和产气，降低电池温度，减缓丙酸乙酯与活性物质的副反应，避免由电芯鼓胀引起的电芯本体变形或爆炸，避免电芯发生正负极短路引起着火，达到提升电池安全的效果。However, due to the addition of a large amount of ethyl propionate to the electrolyte, ethyl propionate has a low boiling point and strong activity. It is unstable in the cell and is easily decomposed by the redox of the active material, thereby releasing a large amount of heat from the reaction and causing the safety performance of the battery to fail. , In this application, a separator containing a non-full coverage coated adhesive layer is used, and a large number of channels are added between the positive electrode and the separator, the negative electrode and the separator inside the battery, and the heat and generated heat in the center of the battery cell can be removed when the battery is in a high temperature environment. gas, reduce the battery temperature, slow down the side reaction between ethyl propionate and active substances, avoid the deformation or explosion of the battery body caused by the swelling of the battery, and avoid the short circuit of the positive and negative poles of the battery to cause fire, so as to improve the safety of the battery.
附图说明Description of drawings
图1：本申请的锂离子电池中隔膜截面示意图。Figure 1: Schematic diagram of the cross-section of the separator in the lithium-ion battery of the present application.
具体实施方式Detailed ways
为使本领域技术人员更好地理解本申请的方案，下面对本申请作进一步地详细说明。In order to enable those skilled in the art to better understand the solution of the present application, the present application will be further described in detail below.
下文将结合具体实施例对本申请做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本申请，而不应被解释为对本申请保护范围的限制。凡基于本申请上述内容所实现的技术均涵盖在本申请旨在保护的范围内。The present application will be further described in detail below in conjunction with specific embodiments. It should be understood that the following examples are only for illustrating and explaining the present application, and should not be construed as limiting the protection scope of the present application. All technologies implemented based on the above contents of the application are covered within the scope of protection intended by the application.
下述实施例中所使用的实验方法如无特殊说明，均为常规方法；下述实施例中所用的试剂、材料等，如无特殊说明，均可从商业途径得到。The experimental methods used in the following examples are conventional methods unless otherwise specified; the reagents and materials used in the following examples can be obtained from commercial sources unless otherwise specified.
对比例1-5和实施例1-8Comparative Examples 1-5 and Examples 1-8
对比例1-5和实施例1-8的锂离子电池均按照下述制备方法进行制备，区别仅在于隔膜和电解液的选择不同，具体区别如表1所示。The lithium-ion batteries of Comparative Examples 1-5 and Examples 1-8 were prepared according to the following preparation methods, the only difference being the choice of diaphragm and electrolyte, the specific differences are shown in Table 1.
(1)正极片制备(1) Preparation of positive electrode sheet
将正极活性物质LiCoO 2、粘结剂聚偏氟乙烯(PVDF)、导电剂乙炔黑按照重量比97.2:1.3:1.5进行混合，加入N-甲基吡咯烷酮(NMP)，在真空搅拌机作用下搅拌，直至混合体系成均一流动性的正极浆料；将正极浆料均匀涂覆于厚度为9～12μm的铝箔上；将上述涂覆好的铝箔在5段不同温度梯度的烘箱烘烤后，再将其在120℃的烘箱干燥8h，然后经过辊压、分切得到所需的正极片。 Mix the positive electrode active material LiCoO 2 , the binder polyvinylidene fluoride (PVDF), and the conductive agent acetylene black at a weight ratio of 97.2:1.3:1.5, add N-methylpyrrolidone (NMP), and stir under the action of a vacuum mixer. Until the mixed system becomes a positive electrode slurry with uniform fluidity; evenly coat the positive electrode slurry on an aluminum foil with a thickness of 9-12 μm; bake the above-mentioned coated aluminum foil in an oven with 5 different temperature gradients, and then It was dried in an oven at 120° C. for 8 hours, and then rolled and cut to obtain the desired positive electrode sheet.
(2)负极片制备(2) Negative sheet preparation
将质量占比为96.5％的人造石墨负极材料，质量占比为0.1％的单壁碳纳米管(SWCNT)导电剂、质量占比为1％的导电炭黑(SP)导电剂、质量占比为1％的羧甲基纤维素钠(CMC)粘结剂及质量占比为1.4％的丁苯橡胶(SBR)粘结剂以湿法工艺制成浆料，涂覆于负极集流体铜箔的表面，经烘干(温度：85℃，时间：5h)、辊压和模切得到负极片。The artificial graphite negative electrode material with a mass proportion of 96.5%, the single-walled carbon nanotube (SWCNT) conductive agent with a mass proportion of 0.1%, the conductive carbon black (SP) conductive agent with a mass proportion of 1%, and the mass proportion A 1% sodium carboxymethylcellulose (CMC) binder and a 1.4% styrene-butadiene rubber (SBR) binder are made into a slurry by a wet process and coated on the negative electrode current collector copper foil The surface was dried (temperature: 85° C., time: 5 h), rolled and die-cut to obtain the negative electrode sheet.
(3)非水电解液制备(3) Preparation of non-aqueous electrolyte
在充满氩气的手套箱(水分<10ppm，氧分<1ppm)中，将碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、丙酸丙酯(PP)以1:1:2质量比混合均匀，在混合溶液中缓慢加入基于非水电解液总质量14wt.％的LiPF 6、基于非水电解液总质量 10～50wt.％的丙酸乙酯(丙酸乙酯的具体用量如表1所示)和添加剂(添加剂的具体用量和选择如表1所示)，搅拌均匀得到非水电解液。 In a glove box filled with argon (moisture <10ppm, oxygen <1ppm), mix ethylene carbonate (EC), propylene carbonate (PC), and propyl propionate (PP) in a mass ratio of 1:1:2 Uniformly, slowly add 14wt.% LiPF 6 based on the total mass of the non-aqueous electrolyte to the mixed solution, and 10-50 wt.% ethyl propionate based on the total mass of the non-aqueous electrolyte (the specific amount of ethyl propionate is shown in Table 1 shown) and additives (the specific dosage and selection of additives are shown in Table 1), and stirred evenly to obtain non-aqueous electrolyte.
(4)隔膜的制备(4) Preparation of diaphragm
在厚度为5μm的聚乙烯基材的第一表面涂覆一层厚度为2μm的陶瓷层(陶瓷层的组成为：91wt％的氧化铝、4.5wt％的聚甲基丙烯酸甲酯、4.5wt％的羧甲基纤维素钠)，在聚乙烯基材的第二表面和陶瓷层表面各涂覆一层厚度为1μm的涂胶层，所述涂胶层均为非全覆盖涂覆，即所述涂胶层包括涂胶区和非涂胶区，且所述涂胶区和非涂胶区彼此相邻设置，所述涂胶区内涂覆涂胶，所述非涂胶区内不涂覆涂胶，所述涂胶为聚偏氟乙烯-六氟丙烯共聚物。所述涂胶区的幅宽为1mm～5mm，所述非涂胶区的幅宽为0.5mm～2mm(具体幅宽如表1所示)。The first surface of the polyethylene substrate with a thickness of 5 μm is coated with a ceramic layer with a thickness of 2 μm (the composition of the ceramic layer is: 91wt% aluminum oxide, 4.5wt% polymethyl methacrylate, 4.5wt% Sodium carboxymethyl cellulose), on the second surface of the polyethylene substrate and the surface of the ceramic layer, respectively coat a layer of glue coating with a thickness of 1 μm, and the glue coating is all non-full coverage coating, that is, the The glue-coated layer includes a glue-coated area and a non-glue-coated area, and the glue-coated area and the non-glue-coated area are arranged adjacent to each other, the glue-coated area is coated with glue, and the non-glued area is not coated. Overcoat glue, said glue is polyvinylidene fluoride-hexafluoropropylene copolymer. The width of the glue-coated area is 1mm-5mm, and the width of the non-glue-coated area is 0.5mm-2mm (the specific width is shown in Table 1).
(5)锂离子电池的制备(5) Preparation of lithium ion battery
将上述准备的正极片、隔膜、负极片通过卷绕得到未注液的裸电芯；将裸电芯置于外包装箔中，将上述制备好的电解液注入到干燥后的裸电芯中，经过真空封装、静置、化成、整形、分选等工序，获得所需的锂离子电池。Wind the above-prepared positive electrode sheet, separator, and negative electrode sheet to obtain a bare cell without liquid injection; place the bare cell in the outer packaging foil, and inject the above-mentioned prepared electrolyte into the dried bare cell , after vacuum packaging, standing, forming, shaping, sorting and other processes, the required lithium-ion batteries are obtained.
表1对比例1-5和实施例1-8制备得到的锂离子电池Lithium-ion batteries prepared by Table 1 Comparative Examples 1-5 and Examples 1-8
Figure PCTCN2022096946-appb-000005
Figure PCTCN2022096946-appb-000005
表中：A为4-甲基-1,2-氧硫杂环戊烷-2,2-二氧化物；B为三(2-氰乙基)硼酸酯；C为三甲基硅基取代甲基磺酰胺类化合物；具体地，D为式1-1所示物质；E为式1-2所示物质；全涂覆隔膜是指涂层中全部涂覆涂胶。In the table: A is 4-methyl-1,2-oxathiolane-2,2-dioxide; B is tris(2-cyanoethyl) borate; C is trimethylsilyl Substituted methylsulfonamide compounds; specifically, D is the substance shown in formula 1-1; E is the substance shown in formula 1-2; fully coated separator means that the coating is completely coated with glue.
Figure PCTCN2022096946-appb-000006
Figure PCTCN2022096946-appb-000006
对上述对比例和实施例所得电池进行电化学性能测试，相关说明如下：Electrochemical performance test is carried out to the battery obtained in the above-mentioned comparative examples and examples, and the relevant instructions are as follows:
45℃循环实验：将上述实施例和对比例所得电池置于(45±2)℃环境中，静置2-3个小时，待电池本体达到(45±2)℃时，电池按照1C恒流充电截止电流为0.05C，电池充满电后搁置5min，再以0.7C恒流放电至截止电压3.0V，记录前3次循环的最高放电容量为初始容量Q，当循环达到400次数时，记录电池的最后一次的放电容量Q 1，记录结果如表2。 45°C cycle test: Place the batteries obtained in the above examples and comparative examples in an environment of (45±2)°C, and let them stand for 2-3 hours. The charging cut-off current is 0.05C. After the battery is fully charged, it is set aside for 5 minutes, and then discharged at a constant current of 0.7C to a cut-off voltage of 3.0V. The highest discharge capacity of the first 3 cycles is recorded as the initial capacity Q. When the cycle reaches 400 times, record the battery Table 2 shows the results of the last discharge capacity Q 1 .
其中用到的计算公式如下：容量保持率(％)＝Q 1/Q×100％。 The calculation formula used therein is as follows: capacity retention rate (%)=Q 1 /Q×100%.
130℃热冲击实验：将上述实施例和对比例所得电池用对流方式或循环热空气箱以起始温度25±3℃进行加热，温变率5±2℃/min，升温至130±2℃，保持60min后结束试验，记录电池状态结果如表2。130°C thermal shock test: Heat the batteries obtained in the above examples and comparative examples with a convection method or a circulating hot air box at an initial temperature of 25±3°C, with a temperature change rate of 5±2°C/min, and then heat up to 130±2°C , keep the test for 60 minutes and end the test, record the battery status results as shown in Table 2.
低温放电实验：将上述实施例和对比例所得电池在环境温度25±3℃，先以0.2C放电至3.0V，搁置5min；以0.7C充电，当电芯端电压达到充电限制电压时，改为恒压充电，直到充电电流≤截止电流，停止充电，搁置5分钟后，以0.2C放电至3.0V，记录此次放电容量为常温容量Q 2。然后电芯以0.7C充电，当电芯端电压达到充电限制电压时，改为恒压充电，直到充电电流小于或等于截止电流，停止充电；将充满电的电池在-10±2℃条件下搁置4h后，以0.3C电流放电至截止电压3.0V，记录放电容量Q 3，计算可得低温放电容量保持率，记录结果如表2。 Low-temperature discharge experiment: Discharge the batteries obtained in the above examples and comparative examples at an ambient temperature of 25±3°C to 3.0V at 0.2C and leave it for 5 minutes; Charge at constant voltage until the charging current ≤ cut-off current, stop charging, and then discharge to 3.0V at 0.2C after standing aside for 5 minutes, record the discharge capacity as room temperature capacity Q 2 . Then the cell is charged at 0.7C. When the terminal voltage of the cell reaches the charging limit voltage, it is changed to constant voltage charging until the charging current is less than or equal to the cut-off current, and the charging is stopped; the fully charged battery is kept at -10±2°C After resting for 4 hours, discharge at a current of 0.3C to a cut-off voltage of 3.0V, record the discharge capacity Q 3 , and calculate the low-temperature discharge capacity retention rate. The recorded results are shown in Table 2.
其中用到的计算公式如下：低温放电容量保持率(％)＝Q 3/Q 2×100％。 The calculation formula used therein is as follows: low-temperature discharge capacity retention rate (%)=Q 3 /Q 2 ×100%.
表2对比例1-5和实施例1-8所得电池实验测试结果Table 2 comparative example 1-5 and embodiment 1-8 gained battery experiment test result
Figure PCTCN2022096946-appb-000007
Figure PCTCN2022096946-appb-000007
由表2结果可以看出：通过对比例和实施例可以看出，电解液中加入添加剂4-甲基-1,2-氧硫杂环戊烷-2,2-二氧化物、三(2-氰乙基)硼酸酯和三甲基硅基取代甲基磺酰胺类化合物以及丙酸乙酯溶剂配合非全覆盖涂覆胶隔膜的优化组合能够明显改善锂离子电池安全性能，同时兼具良好的低温放电性能。As can be seen from the results in Table 2: as can be seen from the comparative examples and examples, the addition of additives 4-methyl-1,2-oxathiolane-2,2-dioxide, tris(2 The optimal combination of -cyanoethyl) borate and trimethylsilyl-substituted methylsulfonamide compounds and ethyl propionate solvent with a non-full coverage coating separator can significantly improve the safety performance of lithium-ion batteries, and at the same time Good low temperature discharge performance.
以上，对本申请的实施方式进行了说明。但是，本申请不限定于上述实施方式。凡在本申请的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。The embodiments of the present application have been described above. However, this application is not limited to the above-mentioned embodiment. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of this application shall be included within the protection scope of this application.

Claims (17)

  1. 一种锂离子电池，其包括正极片、负极片、置于正极片和负极片之间的隔膜，以及非水电解液；A lithium ion battery comprising a positive electrode sheet, a negative electrode sheet, a separator placed between the positive electrode sheet and the negative electrode sheet, and a non-aqueous electrolyte;
    所述隔膜包括基材、陶瓷层、第一涂胶层和第二涂胶层，所述陶瓷层涂覆在基材的第一表面，所述第一涂胶层涂覆在基材的与第一表面相对的第二表面，所述第二涂胶层涂覆在陶瓷层表面；The diaphragm includes a base material, a ceramic layer, a first glue layer and a second glue layer, the ceramic layer is coated on the first surface of the base material, and the first glue layer is coated on the base material and the second glue layer. a second surface opposite to the first surface, the second glue layer is coated on the surface of the ceramic layer;
    所述非水电解液包括非水有机溶剂、添加剂和锂盐，其中所述非水有机溶剂包括丙酸乙酯；所述添加剂包括4-甲基-1,2-氧硫杂环戊烷-2,2-二氧化物、三(2-氰乙基)硼酸酯和至少一种式1所示的三甲基硅基取代甲基磺酰胺类化合物；The non-aqueous electrolytic solution includes a non-aqueous organic solvent, an additive and a lithium salt, wherein the non-aqueous organic solvent includes ethyl propionate; the additive includes 4-methyl-1,2-oxathiolane- 2,2-dioxide, tris(2-cyanoethyl) borate and at least one trimethylsilyl-substituted methylsulfonamide compound represented by formula 1;
    Figure PCTCN2022096946-appb-100001
    Figure PCTCN2022096946-appb-100001
    式1中，R选自芳基或
    Figure PCTCN2022096946-appb-100002
    n为1～6之间的整数，*为连接点。     In formula 1, R is selected from aryl or
    Figure PCTCN2022096946-appb-100002
    n is an integer between 1 and 6, and * is a connection point.
  2. 根据权利要求1所述的锂离子电池，其中，所述式1所示的三甲基硅基取代甲基磺酰胺类化合物选自如下式1-1和式1-2中的至少一种：The lithium ion battery according to claim 1, wherein the trimethylsilyl-substituted methylsulfonamide compound shown in the formula 1 is selected from at least one of the following formula 1-1 and formula 1-2:
    Figure PCTCN2022096946-appb-100003
    Figure PCTCN2022096946-appb-100003
  3. 根据权利要求1或2所述的锂离子电池，其中，所述4-甲基-1,2-氧硫 杂环戊烷-2,2-二氧化物的添加量为非水电解液总质量的1～3wt.％。The lithium-ion battery according to claim 1 or 2, wherein the added amount of the 4-methyl-1,2-oxathiolane-2,2-dioxide is the total mass of the non-aqueous electrolyte 1 ~ 3wt.% of.
  4. 根据权利要求1或2所述的锂离子电池，其中，所述三(2-氰乙基)硼酸酯的添加量为非水电解液总质量的0.5～3.5wt.％。The lithium ion battery according to claim 1 or 2, wherein the added amount of the tris (2-cyanoethyl) borate is 0.5-3.5 wt.% of the total mass of the non-aqueous electrolyte.
  5. 根据权利要求1或2所述的锂离子电池，其中，所述式1所示的三甲基硅基取代甲基磺酰胺类化合物的添加量为非水电解液总质量的0.2～1.8wt.％。The lithium ion battery according to claim 1 or 2, wherein the addition amount of the trimethylsilyl-substituted methylsulfonamide compound shown in the formula 1 is 0.2 to 1.8wt. of the total mass of the non-aqueous electrolyte. %.
  6. 根据权利要求1-5任一项所述的锂离子电池，其中，所述丙酸乙酯的添加量为非水电解液总质量的10～50wt.％。The lithium ion battery according to any one of claims 1-5, wherein the added amount of the ethyl propionate is 10-50wt.% of the total mass of the non-aqueous electrolyte.
  7. 根据权利要求1-6任一项所述的锂离子电池，其中，所述陶瓷层包括陶瓷、粘结剂和增稠剂。The lithium ion battery according to any one of claims 1-6, wherein the ceramic layer comprises ceramics, a binder and a thickener.
  8. 根据权利要求1-6任一项所述的锂离子电池，其中，所述陶瓷层包括如下质量百分含量的各组分：85～97wt％的陶瓷、1～10wt％的粘结剂和0.5～10wt％的增稠剂。The lithium ion battery according to any one of claims 1-6, wherein the ceramic layer comprises the following components in mass percentage: 85-97wt% of ceramics, 1-10wt% of binder and 0.5 ~10 wt% thickener.
  9. 根据权利要求1-8任一项所述的锂离子电池，其中，所述第一涂胶层包括若干彼此相邻设置的第一涂胶区和第一非涂胶区，所述第一涂胶区内涂覆第一涂胶，所述第一非涂胶区内不涂覆第一涂胶。The lithium-ion battery according to any one of claims 1-8, wherein the first glue-coating layer comprises several first glue-coating regions and first non-glue-coating regions arranged adjacent to each other, and the first glue-coating The first glue is coated in the glue area, and the first glue is not coated in the first non-glue area.
  10. 根据权利要求1-8任一项所述的锂离子电池，其中，所述第二涂胶层包括若干彼此相邻设置的第二涂胶区和第二非涂胶区，所述第二涂胶区内涂覆第二涂胶，所述第二非涂胶区内不涂覆第二涂胶。The lithium-ion battery according to any one of claims 1-8, wherein the second glue layer comprises several second glue-coated regions and second non-glue-coated regions arranged adjacent to each other, the second glue-coated The second glue is coated in the glue area, and the second glue is not coated in the second non-glue area.
  11. 根据权利要求1-10任一项所述的锂离子电池，其中，所述第一涂胶层为非全覆盖涂覆，即第一涂胶区和第一非涂胶区彼此相邻设置，且所述第一涂胶区的幅宽为1mm～5mm，所述第一非涂胶区的幅宽为0.5mm～2mm。The lithium-ion battery according to any one of claims 1-10, wherein the first glue-coated layer is non-full-coverage coating, that is, the first glue-coated area and the first non-glue-coated area are arranged adjacent to each other, And the width of the first glue-coated area is 1mm-5mm, and the width of the first non-glue-coated area is 0.5mm-2mm.
  12. 根据权利要求1-10任一项所述的锂离子电池，其中，所述第二涂胶层为非全覆盖涂覆，即第二涂胶区和第二非涂胶区彼此相邻设置，且所述第二涂胶区的幅宽为1mm～5mm，所述第二非涂胶区的幅宽为0.5mm～2mm。The lithium-ion battery according to any one of claims 1-10, wherein the second glue layer is not fully covered, that is, the second glue-coated area and the second non-glue-coated area are arranged adjacent to each other, And the width of the second glue-coated area is 1mm-5mm, and the width of the second non-glue-coated area is 0.5mm-2mm.
  13. 根据权利要求1-12任一项所述的锂离子电池，其中，所述陶瓷层的厚度为1～5μm。The lithium ion battery according to any one of claims 1-12, wherein the thickness of the ceramic layer is 1-5 μm.
  14. 根据权利要求1-12任一项所述的锂离子电池，其中，所述第一涂胶层的厚度为0.5～2μm。The lithium ion battery according to any one of claims 1-12, wherein the thickness of the first adhesive layer is 0.5-2 μm.
  15. 根据权利要求1-12任一项所述的锂离子电池，其中，所述第二涂胶 层的厚度为0.5～2μm。The lithium ion battery according to any one of claims 1-12, wherein the thickness of the second adhesive layer is 0.5-2 μm.
  16. 根据权利要求1-15任一项所述的锂离子电池，其中，所述正极片包括正极集流体和涂覆在正极集流体一侧或两侧表面的正极活性物质层，所述正极活性物质层包括正极活性物质、导电剂和粘结剂，The lithium ion battery according to any one of claims 1-15, wherein the positive electrode sheet comprises a positive electrode current collector and a positive electrode active material layer coated on one or both sides of the positive electrode current collector, the positive electrode active material The layer includes positive electrode active material, conductive agent and binder,
    所述的正极活性物质选自钴酸锂或经过Al、Mg、Mn、Cr、Ti、Zr中两种或多种元素掺杂包覆处理的钴酸锂，所述经过Al、Mg、Mn、Cr、Ti、Zr中两种或多种元素掺杂包覆处理的钴酸锂的化学式为Li xCo 1-y1-y2-y3-y4A y1B y2C y3D y4O 2；0.95≤x≤1.05，0.01≤y1≤0.1，0.01≤y2≤0.1，0≤y3≤0.1，0≤y4≤0.1，A、B、C、D选自Al、Mg、Mn、Cr、Ti、Zr中两种或多种元素。 The positive electrode active material is selected from lithium cobaltate or lithium cobaltate that has been doped and coated with two or more elements in Al, Mg, Mn, Cr, Ti, and Zr. The chemical formula of lithium cobalt oxide coated with two or more elements in Cr, Ti, Zr is Li x Co 1-y1-y2-y3-y4 A y1 B y2 C y3 D y4 O 2 ; 0.95≤x ≤1.05, 0.01≤y1≤0.1, 0.01≤y2≤0.1, 0≤y3≤0.1, 0≤y4≤0.1, A, B, C, D are selected from two of Al, Mg, Mn, Cr, Ti, Zr or multiple elements.
  17. 根据权利要求1-16任一项所述的锂离子电池，其中，所述负极片包括负极集流体和涂覆在负极集流体一侧或两侧表面的负极活性物质层，所述负极活性物质层包括负极活性物质、导电剂和粘结剂，The lithium ion battery according to any one of claims 1-16, wherein the negative electrode sheet comprises a negative electrode current collector and a negative electrode active material layer coated on one or both sides of the negative electrode current collector, the negative electrode active material The layer includes negative electrode active material, conductive agent and binder,
    所述的负极活性物质选自石墨或含1～12wt％SiOx/C或Si/C的石墨复合材料。The negative electrode active material is selected from graphite or graphite composite material containing 1-12wt% SiOx/C or Si/C.
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