WO2017217769A1 - Électrode pour batterie secondaire et batterie secondaire au lithium comprenant celle-ci - Google Patents

Électrode pour batterie secondaire et batterie secondaire au lithium comprenant celle-ci Download PDF

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Publication number
WO2017217769A1
WO2017217769A1 PCT/KR2017/006213 KR2017006213W WO2017217769A1 WO 2017217769 A1 WO2017217769 A1 WO 2017217769A1 KR 2017006213 W KR2017006213 W KR 2017006213W WO 2017217769 A1 WO2017217769 A1 WO 2017217769A1
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Prior art keywords
active material
electrode active
electrode
material layer
secondary battery
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PCT/KR2017/006213
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English (en)
Korean (ko)
Inventor
민지원
하회진
윤종건
김석구
윤여경
될레야니스
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주식회사 엘지화학
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Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2018528989A priority Critical patent/JP2019501492A/ja
Priority to CN201780003721.XA priority patent/CN108352504B/zh
Priority to US15/768,987 priority patent/US10873105B2/en
Priority to EP17813592.7A priority patent/EP3451421B1/fr
Priority to PL17813592T priority patent/PL3451421T3/pl
Priority claimed from KR1020170074716A external-priority patent/KR102135284B1/ko
Publication of WO2017217769A1 publication Critical patent/WO2017217769A1/fr
Priority to JP2021180200A priority patent/JP7540988B2/ja

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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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 present invention relates to a secondary battery electrode and a lithium secondary battery comprising the same, and more particularly, to a secondary battery electrode and a secondary battery of the secondary battery having a high capacity and stable stability.
  • a secondary battery has a larger capacity per unit area so that a long time use of an electronic device equipped with a secondary battery capable of repetitive charging and discharging is possible.
  • the secondary battery also needs to ensure high stability such that damage or fire does not occur due to external shock or rapid temperature or pressure change.
  • Nail penetration test is a test to check whether secondary batteries generate heat, fire, and explosion by causing sharp objects such as nails to be damaged.
  • the electrode In order to pass the nail penetration test, when a sharp object collides with the secondary battery and damages the secondary battery, the electrode must be cut and shorted. This is because the electrode must be cut so that no fire or explosion occurs.
  • nickel-cobalt-manganese-based lithium oxide has been widely used as an electrode active material of lithium secondary batteries in recent years.
  • high nickel-cobalt-manganese-based lithium oxide having a high nickel content in transition metals is used in medium and large batteries requiring high capacity because of high energy density per unit volume.
  • an electrode using a high concentration of nickel-cobalt-manganese-based lithium oxide as an electrode active material has a problem in that the elongation is large so that the electrode is not easily broken by an external impact and thus the electrode is easily exploded or ignited. The elongation at this time refers to the rate at which the material stretches in the tensile test.
  • the present invention is to solve the above problems, to provide a secondary battery electrode and a lithium secondary battery comprising the same, which has a high capacity and can be excellent evaluation in the nail penetration test.
  • the present invention is an electrode current collector; A first electrode active material layer formed on the electrode current collector; And a second electrode active material layer formed on the first electrode active material layer, and a tensile strain of a layer in which the electrode current collector and the first electrode active material layer are combined is 1.2% or less.
  • the second electrode active material layer preferably has a larger energy density per unit volume than the first electrode active material layer.
  • each of the first electrode active material layer and the second electrode active material layer may include a lithium transition metal oxide as an active material, and specifically, the lithium transition metal oxide may be represented by Formula 1 below. have.
  • the lithium transition metal oxides included in the first electrode active material layer and the second electrode active material layer may have the same or different compositions.
  • the first electrode active material layer and the second electrode coating has a per unit area, the energy density can be 1mAh / cm 2 to 6mAh / cm 2.
  • the first electrode active material layer may have a thickness of 15 ⁇ m to 150 ⁇ m
  • the second electrode active material layer may have a thickness of 15 ⁇ m to 100 ⁇ m.
  • the electrode according to the present invention is laminated on the second electrode active material layer and contains a lithium ion conductive layer containing a lithium ion conductive gel swollen with a nonaqueous electrolyte solution and a surface of the lithium ion conductive layer.
  • the laminate may further include a porous heat resistant layer containing insulating metal oxide particles.
  • the electrode may be an anode.
  • the present invention provides a lithium secondary battery comprising the electrode according to the present invention as described above.
  • the electrode of the present invention includes two layers of the electrode active material layer, so that the electrode active material layer may include a relatively large amount of the active material compared to the electrode provided with one layer, while peeling from the current collector, migration of the binder, and the like. It is possible to achieve high capacity stably by not generating.
  • the electrode of the present invention forms an active material layer having a low elongation as the first electrode active material layer provided on the side close to the current collector, so that when the external impact is applied, it is possible to implement excellent stability by increasing the electrode fracture resistance.
  • FIG. 1 is a view showing an electrode for a secondary battery according to an embodiment of the present invention.
  • FIG. 2 is a view illustrating a nail penetration test performed on the secondary battery electrode according to the exemplary embodiment of the present invention.
  • FIG. 3 is a view showing the state of the electrode after the nail penetration test on the secondary battery electrode according to an embodiment of the present invention.
  • FIG. 4 is a view illustrating an electrode for a secondary battery according to another embodiment of the present invention.
  • FIG. 5 is a graph showing the elongation of the layer of the current collector and the first electrode active material layer prepared according to Preparation Examples 1 to 3.
  • FIG. 6 is a view showing an elongation measuring device of the present invention.
  • FIG. 1 is a view showing an electrode for a secondary battery according to an embodiment of the present invention.
  • an electrode E for a secondary battery may include an electrode current collector 10, a first electrode active material layer 20 formed on the electrode current collector 10, and the And a second electrode active material layer 30 formed on the first electrode active material layer.
  • FIG. 1 illustrates a case in which an electrode active material layer is stacked only on one surface of the electrode current collector 10, but is not limited thereto.
  • the electrode current collector 10 of the electrode E according to an embodiment of the present invention may be formed.
  • the electrode active material layer may be laminated on both surfaces.
  • electrode current collectors generally used in the art may be used, and the electrode current collector 10 may be electrically conductive without causing chemical change in the battery, and the type thereof is not particularly limited.
  • the electrode current collector 10 copper, stainless steel, aluminum, nickel, titanium, calcined carbon, surface treated with carbon, nickel, titanium, silver, etc. on the surface of copper or stainless steel, aluminum- Cadmium alloys and the like can be used.
  • fine concavities and convexities may be formed on the surface of the current collector to enhance bonding strength with the active material layer, and may be used in various forms such as films, sheets, foils, nets, porous bodies, foams, and nonwoven fabrics. It may have a thickness.
  • the layer in which the electrode current collector and the first electrode active material layer 20 are combined has an elongation of 1.2% or less, preferably 1.0% or less.
  • the elongation refers to the rate at which the material is stretched in the tensile test, the larger the elongation material is a property that does not break against the external impact is greater. In other words, the elongation is used as a measure of the fracture performance of the material. Therefore, a material with a small elongation tends to be broken by an external impact, and a material with a large elongation is largely extended without breaking by an external impact.
  • the elongation is influenced by the material and thickness of the current collector, the thickness of the first electrode active material layer, the composition of the slurry constituting the first electrode active material layer, the type of active material used, the particle size of the active material, and the like. Accordingly, by appropriately adjusting the above factors, the elongation of the combined layer of the electrode current collector and the first electrode active material layer may be obtained in a desired range.
  • the elongation of the layer in which the electrode current collector and the first electrode active material layer are combined may be measured by the following method. First, a slurry for forming a first electrode active material layer is applied to an electrode current collector, and then dried to prepare a sample having a size of 15 mm (W) X 150 mm (L). Then, the sample is mounted on the sample grip part of the elongation measuring device (for example, Instron 3345 UTM) as shown in FIG. 6, and then the tensile strain is measured while pulling at a speed of 5 mm / min. The tensile strain just before breaking is set to elongation.
  • the elongation measuring device for example, Instron 3345 UTM
  • the current collector and the first electrode active material layer are easily broken and short-circuited. It can effectively prevent ignition or explosion.
  • FIG. 2 is a view showing a nail penetration test on the secondary battery electrode according to an embodiment of the present invention
  • Figure 3 is a nail penetration test on the secondary battery electrode according to an embodiment of the present invention after It is a figure which shows the state of an electrode. 2 and 3 to describe the technical effects of the electrode for secondary batteries according to an embodiment of the present invention in the nail penetration test.
  • the secondary battery needs to ensure high stability so that the secondary battery does not cause damage or fire due to external shock or rapid internal temperature or pressure change.
  • the nail penetration test is a test for checking whether a secondary battery generates heat, fire, or explosion when a sharp object such as a nail is damaged. To pass the nail penetration test, the electrode must be cut when a sharp object penetrates the secondary battery and damages the secondary battery. This is because the electrode must be cut so that no fire or explosion occurs.
  • the electrode active material layer or the electrode current collector needs to be easily cut when a sharp material penetrates the electrode from the outside. Therefore, in order to pass the nail penetration test, the smaller the elongation of the electrode active material layer is, the better. The smaller the elongation, the easier it is to break.
  • an elongation of a layer in which the first electrode active material layer 20 having a small elongation is laminated adjacently on the electrode current collector 10 and the electrode current collector 10 and the first electrode active material layer 20 are combined
  • the 1.2% or less so that the cutting of the electrode in the nail penetration test or real life can easily occur as shown in FIG. That is, when the nail 100 penetrates into the electrode E according to an embodiment of the present invention in a nail penetration test or real life, the electrode active material layers and the entire electrode current collector are cut as shown in FIG. It can block the risk of overheating, fire or explosion.
  • the electrode of the present invention is composed of two layers of the electrode active material, thereby increasing the selectivity of the material that can be used for the second electrode active material layer 30, thereby improving the freedom of design of the electrode.
  • the present invention is not limited thereto, but the energy density per unit area of the second electrode active material layer 30 may be greater than the energy density per unit area of the first electrode active material layer 20, and in this case, the electrode active material Compared with the case where the layer is composed of one layer, a secondary battery having better capacity characteristics than the same volume may be manufactured. That is, in the present invention, the electrode active material layer is formed in a two-layer structure, and the elongation of the electrode current collector and the first electrode active material layer formed on the electrode current collector, which are layers affecting the electrode breakability, are adjusted to a specific range, and the second By forming an active material layer having excellent capacity characteristics in the electrode active material layer, it is possible to form an electrode having high stability and excellent stability.
  • the first electrode active material layer has an energy density per unit area of 1 to 6 mAh / cm 2 , preferably 1 to 5 mAh / cm 2 , and more preferably 1 to 4 mAh / cm 2.
  • the second electrode active material layer may have an energy density of 1 to 6 mAh / cm 2 , preferably 2 to 6 mAh / cm 2 , and more preferably 3 to 6 mAh / cm 2 per unit area.
  • the first electrode active material layer and the second electrode active material layer may be suitably used in a medium-large-capacity high capacity battery cell, and the loading amount per electrode weight may be lowered to obtain an effect of thinning the electrode thickness.
  • the first electrode active material layer and the second electrode active material layer include a lithium transition metal oxide as the active material.
  • the lithium transition metal oxide may be nickel-cobalt-manganese-based lithium metal oxide represented by the following Chemical Formula 1.
  • the nickel-cobalt-manganese-based lithium metal oxide represented by Chemical Formula 1 is an nickel-cobalt-manganese electrode active material including 50 mol% or more of nickel in the transition metal.
  • the greater the amount of nickel in the electrode active material the greater the energy density per unit volume, which has the advantage of producing a battery having a large electric capacity.
  • the lithium transition metal oxide is Li [Ni 0.6 CO 0.2 Mn 0.2 ] O 2 , Li [Ni 0.8 CO 0.1 Mn 0.1 ] O 2 Etc., but is not limited thereto.
  • the lithium transition metal oxides included in the first electrode active material layer and the second electrode active material layer may have the same or different compositions.
  • all of the active materials included in the first electrode active material layer and the second electrode active material layer may be nickel-cobalt-manganese-based lithium metal oxides.
  • nickel, cobalt, and manganese contained in the lithium transition metal oxides may be used.
  • the content of may be the same or different from each other.
  • the active materials included in the first electrode active material layer and the second electrode active material layer need only be the same kind of components, and the contents of the respective components do not have to be the same.
  • first electrode active material layer and the second electrode active material layer may further include a binder, a conductive material, a dispersant, and the like, as necessary.
  • the binder may be polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethyl methacrylate (polymethylmethacrylate).
  • PVDF-co-HFP polyvinylidene fluoride-hexafluoropropylene copolymer
  • PVDF polyvinylidene fluoride
  • PVDF polyacrylonitrile
  • polymethyl methacrylate polymethylmethacrylate
  • Polyvinyl alcohol Polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, ethylene-propylene-diene monomer (EPDM ), Sulfonated EPDM, styrene butadiene rubber (SBR), fluorine rubber, poly acrylic acid and polymers in which hydrogen thereof is replaced with Li, Na, or Ca, or Various kinds of binder polymers such as various copolymers can be used.
  • CMC carboxymethyl cellulose
  • SBR Sulfonated EPDM
  • SBR styrene butadiene rubber
  • fluorine rubber poly acrylic acid and polymers in which hydrogen thereof is replaced with Li, Na, or Ca
  • binder polymers such as various copolymers can be used.
  • the conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • Examples of the conductive material include graphite such as natural graphite and artificial graphite; Carbon blacks such as acetylene black, Ketjen black, channel black, farnes black, lamp black and thermal black; Conductive fibers such as carbon fibers and metal fibers; Conductive tubes such as carbon nanotubes; Metal powders such as fluorocarbon, aluminum and nickel powders; Conductive whiskers such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • the dispersant may be an aqueous dispersant or an organic dispersant such as N-methyl-2-pyrrolidone.
  • the first electrode active material layer may have a thickness of 15 ⁇ m to 150 ⁇ m
  • the second electrode active material layer may have a thickness of 15 ⁇ m to 100 ⁇ m.
  • the electrode according to the present invention may further include a lithium ion conductive layer and a porous heat resistant layer on the second electrode active material layer as necessary.
  • FIG. 4 is a view illustrating an electrode for a secondary battery according to another embodiment of the present invention.
  • the secondary battery electrode E may include components that are further stacked on the plurality of electrode active material layers. That is, the secondary battery electrode E is laminated on the surface of the electrode active material layer and is formed on the surface of the lithium ion conductive layer 40 and the surface of the lithium ion conductive layer 40 containing the lithium ion conductive gel swelled with a nonaqueous electrolyte.
  • the stack may include a porous heat resistant layer 50 containing insulating metal oxide particles.
  • the porous heat resistant layer 50 serves to prevent the temperature from rising when an internal short circuit occurs in the secondary battery to which the electrode according to the exemplary embodiment of the present invention is applied.
  • some problems may occur when the porous heat-resistant layer 50 is laminated in direct contact with the electrode active material layer. That is, when the porous heat resistant layer 50 is stacked in direct contact with the electrode active material layer, the insulating particles constituting the porous heat resistant layer 50 may flow into the pores in the electrode active material layer, which causes the electrolyte solution to the electrode active material layer.
  • the permeability of may decrease and may lead to a decrease in ion conductivity of the electrode active material layer.
  • the intergranular conductivity in the electrode active material layer may also be lowered, thereby lowering the load characteristics of the secondary battery on which the electrode is mounted.
  • pinholes are easily generated in the porous heat-resistant layer due to irregularities on the surface of the electrode active material layer formed by particles of the electrode active material, a problem may occur in that the stability of the secondary battery is lowered.
  • the configuration for solving this is the lithium ion conductive layer 40. That is, after the lithium ion conductive layer 40 is laminated on the electrode active material layer, the porous heat resistant layer 50 is laminated thereon, thereby preventing the occurrence of pinholes in the porous heat resistant layer 50, while the electrode active material The insulating particles can be prevented from flowing into the gaps between the particles.
  • the electrode according to the present invention can be used as an electrode for a lithium secondary battery, in particular, it can be usefully used as a positive electrode for a lithium secondary battery.
  • the lithium secondary battery includes a positive electrode, a negative electrode positioned to face the positive electrode, a separator and an electrolyte interposed between the positive electrode and the negative electrode, wherein the positive electrode may be the electrode according to the present invention described above.
  • the secondary battery may further include a battery container for accommodating the electrode assembly of the positive electrode, the negative electrode, and the separator, and a sealing member for sealing the battery container. Since the configuration of the anode is the same as described above, a detailed description thereof will be omitted.
  • the negative electrode includes an electrode current collector and a negative electrode active material layer positioned on at least one surface of the electrode current collector.
  • the electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
  • the electrode current collector may be formed on the surface of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper, or stainless steel. Surface-treated with carbon, nickel, titanium, silver, and the like, aluminum-cadmium alloy and the like can be used.
  • the negative electrode current collector may have a thickness of 3 ⁇ m to 500 ⁇ m, and similarly to the positive electrode current collector, fine concavities and convexities may be formed on the surface of the current collector to enhance the bonding force of the negative electrode active material.
  • it can be used in various forms, such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven body.
  • the negative electrode active material layer includes a negative electrode active material, and optionally further includes at least one of a binder, a conductive material, and a dispersant.
  • a compound capable of reversible intercalation and deintercalation of lithium may be used.
  • Specific examples include carbonaceous materials such as artificial graphite, natural graphite, graphitized carbon fibers, and amorphous carbon;
  • Metallic compounds capable of alloying with lithium such as Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si alloys, Sn alloys or Al alloys;
  • a composite including the metallic compound and the carbonaceous material such as a Si-C composite or a Sn-C composite, and any one or a mixture of two or more thereof may be used.
  • a metal lithium thin film may be used as the anode active material.
  • the carbon material both low crystalline carbon and high crystalline carbon can be used. Soft crystalline carbon and hard carbon are typical low crystalline carbon, and high crystalline carbon is amorphous, plate, scaly, spherical or fibrous natural graphite or artificial graphite, Kish graphite (Kish) graphite, pyrolytic carbon, mesophase pitch based carbon fiber, meso-carbon microbeads, mesophase pitches and petroleum or coal tar pitch High-temperature calcined carbon such as derived cokes is typical.
  • the binder, the conductive material and the dispersant may be the same as described above.
  • the separator is to separate the negative electrode and the positive electrode and to provide a passage for the movement of lithium ions, if it is usually used as a separator in a lithium secondary battery can be used without particular limitation, in particular to the ion movement of the electrolyte It is desirable to have a low resistance against the electrolyte and excellent electrolytic solution-moisture capability.
  • a porous polymer film for example, a porous polymer film made of a polyolefin-based polymer such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate copolymer or the like Laminate structures of two or more layers may be used.
  • a porous nonwoven fabrics such as nonwoven fabrics made of high melting point glass fibers, polyethylene terephthalate fibers and the like may be used.
  • a coated separator containing a ceramic component or a polymer material may be used to secure heat resistance or mechanical strength, and may be optionally used as a single layer or a multilayer structure.
  • examples of the electrolyte used in the present invention include an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel polymer electrolyte, a solid inorganic electrolyte, a molten inorganic electrolyte, and the like, which can be used in manufacturing a lithium secondary battery. It doesn't happen.
  • the electrolyte may include an organic solvent and a lithium salt.
  • the organic solvent may be used without particular limitation as long as it can serve as a medium through which ions involved in the electrochemical reaction of the battery can move.
  • the organic solvent may be an ester solvent such as methyl acetate, ethyl acetate, ⁇ -butyrolactone or ⁇ -caprolactone; Ether solvents such as dibutyl ether or tetrahydrofuran; Ketone solvents such as cyclohexanone; Aromatic hydrocarbon solvents such as benzene and fluorobenzene; Dimethylcarbonate (DMC), diethylcarbonate (DEC), methylethylcarbonate (MEC), ethylmethylcarbonate (EMC), ethylene carbonate (EC), propylene carbonate, Carbonate solvents such as PC); Alcohol solvents such as ethyl alcohol and isopropyl alcohol; Nitriles, such as Ra-CN (Ra is a C2-C20 linear, branched, or ring-shaped hydrocarbon group, and may
  • carbonate-based solvents are preferable, and cyclic carbonates having high ionic conductivity and high dielectric constant (for example, ethylene carbonate or propylene carbonate) that can improve the charge and discharge performance of a battery, and low viscosity linear carbonate compounds (for example, a mixture of ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate and the like is more preferable.
  • cyclic carbonate and the chain carbonate are mixed and used in a volume ratio of about 1: 1 to 9, the performance of the electrolyte may be excellent.
  • the lithium salt may be used without particular limitation as long as it is a compound capable of providing lithium ions used in a lithium secondary battery.
  • the lithium salt is LiPF 6 , LiClO 4 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAl0 4 , LiAlCl 4 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiN (C 2 F 5 SO 3 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) 2 .
  • LiCl, LiI, or LiB (C 2 O 4 ) 2 and the like can be used.
  • the concentration of the lithium salt is preferably used within the range of 0.1M to 2.0M. When the concentration of the lithium salt is included in the above range, since the electrolyte has an appropriate conductivity and viscosity, it can exhibit excellent electrolyte performance, and lithium ions can move effectively.
  • the electrolyte includes, in addition to the electrolyte components, haloalkylene carbonate-based compounds such as difluoroethylene carbonate for the purpose of improving the life characteristics of the battery, suppressing the reduction of the battery capacity, and improving the discharge capacity of the battery; Or pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone, N, N
  • One or more additives such as -substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxyethanol or aluminum trichloride may be included. In this case, the additive may be included in an amount of 0.1% by weight to 5% by weight based on the total weight of the electrolyte.
  • the secondary battery according to the present invention may be usefully used in portable devices such as mobile phones, notebook computers, digital cameras, and electric vehicle fields such as hybrid electric vehicles (HEVs).
  • portable devices such as mobile phones, notebook computers, digital cameras, and electric vehicle fields such as hybrid electric vehicles (HEVs).
  • HEVs hybrid electric vehicles
  • the positive electrode active material slurry A was applied to one surface of an aluminum current collector having a thickness of 70 ⁇ m, and then dried at 130 ° C. to form an electrode active material layer.
  • the positive electrode active material slurry B was applied to one surface of an aluminum current collector having a thickness of 70 ⁇ m, and then dried at 130 ° C. to form an electrode active material layer.
  • the positive electrode active material slurry C was applied to one surface of an aluminum current collector having a thickness of 65 ⁇ m, and then dried at 130 ° C. to form an electrode active material layer.
  • Samples having a size of 15 mm (W) X 150 mm (L) were prepared by cutting the current collector on which the electrode active material layers prepared in Preparation Examples 1 to 3 were cut. Then, the sample was mounted on the grip of the Instron 3345 UTM, an elongation measuring device, and the tensile strain was measured while pulling at a speed of 5 mm / min. The measurement result is shown in FIG.
  • the elongation of the current collector prepared using the positive electrode active material slurry A and the electrode active material layer is 1.25%, and the current collector prepared using the positive electrode active material slurry B and the electrode active material layer are combined.
  • the elongation rate of 0.9% and the elongation rate of the layer which combined the electrical power collector and electrode active material layer manufactured using the positive electrode active material slurry C were 1.47%.
  • the positive electrode active material slurry B prepared in Preparation Example 2 was applied on an aluminum current collector in two layers, dried at 130 ° C., and rolled to form a first electrode active material layer formed by the positive electrode active material slurry B and the positive electrode active material slurry B.
  • a positive electrode having a second electrode active material layer was prepared.
  • the positive electrode active material slurry A prepared in Preparation Example 1 was applied on an aluminum current collector in two layers, dried at 130 ° C., and rolled to form a first electrode active material layer formed by the positive electrode active material slurry A and a positive electrode active material slurry A.
  • a positive electrode having a second electrode active material layer was prepared.
  • the positive electrode active material slurry C prepared in Preparation Example 3 was applied on an aluminum current collector in two layers, dried at 130 ° C., and rolled to form a first electrode active material layer formed by the positive electrode active material slurry C and the positive electrode active material slurry C.
  • a positive electrode having a second electrode active material layer was prepared.
  • An electrode assembly was prepared through a porous polyethylene separator between the positive electrode and the negative electrode prepared in Examples 1 to 3 and Comparative Examples 1 to 6, respectively.
  • the negative electrode is a negative electrode active material, natural graphite, carbon black conductive material and PVdF binder in a N-methylpyrrolidone solvent in a ratio of 85: 10: 5 by weight to prepare a composition for forming a negative electrode active material layer, and It was prepared by applying to one surface of a copper current collector.
  • the electrolyte was injected into the case to manufacture a lithium secondary battery.
  • the penetration rate was measured by penetrating a 3 mm nail under a penetration rate of 80 mm / sec and measuring whether or not a fire occurred.
  • the measurement results are shown in Table 1 below. (Circle) and the case where ignition did not occur is represented by X.
  • the lithium secondary batteries using the electrodes of Examples 1 to 3 in which the elongation of the current collector and the first electrode active material layer are 1.2% or less do not ignite in the nail penetration test, and thus have excellent battery stability. can confirm.
  • the case of secondary batteries using the electrodes of Comparative Examples 1 to 6 in which the elongation of the current collector and the first electrode active material layer exceeded 1.2% ignition occurred in the nail penetration test.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention porte également sur une électrode pour une batterie secondaire et sur un procédé de fabrication de l'électrode. Selon la présente invention, une batterie secondaire ayant une stabilité assurée en permettant une excellente évaluation à recevoir dans un test de pénétration de clou tout en ayant une capacité élevée peut être fabriquée. A cet effet, l'invention concerne une électrode pour une batterie secondaire, comprenant : un collecteur de courant; une première couche de matériau actif électrode formée sur le collecteur de courant; et une seconde couche de matériau actif électrode formée sur la première couche de matériau actif électrode, la contrainte de traction de la couche comprenant le collecteur de courant et la première couche de matériau actif électrode étant de 1,2 % ou moins.
PCT/KR2017/006213 2016-06-14 2017-06-14 Électrode pour batterie secondaire et batterie secondaire au lithium comprenant celle-ci WO2017217769A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
JP2018528989A JP2019501492A (ja) 2016-06-14 2017-06-14 二次電池用電極及びこれを含むリチウム二次電池
CN201780003721.XA CN108352504B (zh) 2016-06-14 2017-06-14 二次电池用电极和包含该电极的锂二次电池
US15/768,987 US10873105B2 (en) 2016-06-14 2017-06-14 Electrode for secondary battery and lithium secondary battery including same
EP17813592.7A EP3451421B1 (fr) 2016-06-14 2017-06-14 Électrode pour batterie secondaire et batterie secondaire au lithium comprenant celle-ci
PL17813592T PL3451421T3 (pl) 2016-06-14 2017-06-14 Elektroda do baterii akumulatorowej i zawierająca ją litowa bateria akumulatorowa
JP2021180200A JP7540988B2 (ja) 2016-06-14 2021-11-04 二次電池用電極及びこれを含むリチウム二次電池

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KR10-2016-0073967 2016-06-14
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KR1020170074716A KR102135284B1 (ko) 2016-06-14 2017-06-14 이차전지용 전극 및 이를 포함하는 리튬 이차 전지

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CN112166511A (zh) * 2018-05-24 2021-01-01 24M技术公司 高能量密度组成渐变的电极及其制备方法

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KR20110021974A (ko) * 2009-05-14 2011-03-04 파나소닉 주식회사 리튬이온 이차전지용 전극 및 리튬이온 이차전지
KR20110024114A (ko) * 2009-09-01 2011-03-09 주식회사 엘지화학 못관통 안전성이 향상된 리튬 이차 전지
KR20110107504A (ko) * 2010-03-25 2011-10-04 주식회사 엘지화학 리튬이차전지용 전극 및 이를 포함하는 전지셀
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KR20080070206A (ko) * 2007-01-25 2008-07-30 에스케이에너지 주식회사 리튬 이차 전지
JP5400304B2 (ja) * 2008-01-31 2014-01-29 株式会社オハラ 組電池
KR20110021974A (ko) * 2009-05-14 2011-03-04 파나소닉 주식회사 리튬이온 이차전지용 전극 및 리튬이온 이차전지
KR20110024114A (ko) * 2009-09-01 2011-03-09 주식회사 엘지화학 못관통 안전성이 향상된 리튬 이차 전지
KR20110107504A (ko) * 2010-03-25 2011-10-04 주식회사 엘지화학 리튬이차전지용 전극 및 이를 포함하는 전지셀

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CN112166511A (zh) * 2018-05-24 2021-01-01 24M技术公司 高能量密度组成渐变的电极及其制备方法

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