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WO2018008954A1 - Électrode positive et batterie secondaire la comprenant - Google Patents

Électrode positive et batterie secondaire la comprenant Download PDF

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Publication number
WO2018008954A1
WO2018008954A1 PCT/KR2017/007116 KR2017007116W WO2018008954A1 WO 2018008954 A1 WO2018008954 A1 WO 2018008954A1 KR 2017007116 W KR2017007116 W KR 2017007116W WO 2018008954 A1 WO2018008954 A1 WO 2018008954A1
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WIPO (PCT)
Prior art keywords
pattern
active material
thickness
positive electrode
material particles
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Ceased
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PCT/KR2017/007116
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English (en)
Korean (ko)
Inventor
정혜리
이정필
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LG Chem Ltd
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LG Chem Ltd
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Publication date
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to US15/751,343 priority Critical patent/US10622625B2/en
Priority to JP2018524381A priority patent/JP6763549B2/ja
Priority to PL17824510T priority patent/PL3316358T3/pl
Priority to CN201780004011.9A priority patent/CN108352506B/zh
Priority to EP17824510.6A priority patent/EP3316358B1/fr
Priority claimed from KR1020170085057A external-priority patent/KR101948848B1/ko
Publication of WO2018008954A1 publication Critical patent/WO2018008954A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 positive electrode and a secondary battery including the same, wherein the positive electrode may include a first active material layer, and a first pattern and a second pattern, and the thickness of the first pattern is greater than the thickness of the second pattern. Larger, the volume expansion rate of the second pattern is larger than the volume expansion rate of the first pattern.
  • a representative example of an electrochemical device using such electrochemical energy is a secondary battery, and its use area is gradually increasing.
  • a secondary battery is composed of a positive electrode, a negative electrode, an electrolyte, and a separator, and reciprocates positive and negative electrodes such that lithium ions from the positive electrode active material are inserted into a negative electrode active material such as carbon particles and are detached again when discharged. Since it plays a role of transmitting energy, charging and discharging becomes possible.
  • the amount of active material in the positive electrode is the most important factor in determining the charge / discharge capacity of the battery.
  • positive electrode active materials have been loaded at high levels on the current collector surface.
  • wetting of the electrolyte solution to the active material layer is reduced, and the charge and discharge of the battery such as rapid charging characteristics and output characteristics of the battery due to the difference in reactivity in the electrode thickness direction. Performance is degraded.
  • the impregnation of the electrolyte solution can be improved, the situation that a positive electrode capable of improving the charge and discharge performance of the battery is required.
  • One problem to be solved by the present invention is to provide a positive electrode that can improve the impregnation of the electrolyte, while improving the charge and discharge performance of the battery, while maintaining a high capacity of the battery.
  • Another problem to be solved by the present invention is to improve the stability of the battery.
  • the present invention is a current collector; A first active material layer including first active material particles and disposed on the current collector; And a first pattern and a second pattern that are alternately spaced apart from each other on the first active material layer, wherein the first pattern includes first pattern active material particles, and the second pattern includes second pattern active material particles. And a thickness of the first pattern is greater than a thickness of the second pattern, and a volume expansion rate of the second pattern is greater than a volume expansion rate of the first pattern.
  • the present invention provides a secondary battery including the positive electrode.
  • the positive electrode according to the present invention includes a first pattern and a second pattern in which a part of the high-loaded first active material layer is exposed to the electrolyte and spaced apart from each other, and thus, electrolyte impregnation can be improved, thereby improving charging with high capacity of the battery. Discharge characteristics can be secured.
  • the configuration of the first pattern and the second pattern it is possible to minimize the thickness of the electrode, and to relieve the stress of the electrode generated during charging and discharging with a pattern layer to improve the mechanical stability of the electrode.
  • FIG. 1 is a schematic cross-sectional view of a positive electrode according to an embodiment of the present invention.
  • the terms “comprise”, “comprise” or “have” are intended to indicate that there is a feature, number, step, component, or combination thereof, that is, one or more other features, It should be understood that it does not exclude in advance the possibility of the presence or addition of numbers, steps, components, or combinations thereof.
  • a positive electrode according to an embodiment of the present invention
  • a first active material layer including first active material particles and disposed on the current collector; And a first pattern and a second pattern that are alternately spaced apart from each other on the first active material layer, wherein the first pattern includes first pattern active material particles, and the second pattern includes second pattern active material particles.
  • the thickness of the first pattern may be greater than the thickness of the second pattern, and the volume expansion rate of the second pattern may be greater than the volume expansion rate of the first pattern.
  • the current collector is conductive without causing chemical change in the secondary battery, and includes, for example, copper, stainless steel, aluminum, nickel, titanium, calcined carbon, or carbon, nickel, on the surface of aluminum or stainless steel.
  • the surface-treated with titanium, silver, etc. can be used.
  • the first active material layer may be disposed on the current collector.
  • the first pattern and the second pattern may be disposed on the first active material layer, respectively.
  • the first active material layer 210 may be evenly disposed on the current collector 100 without being spaced apart.
  • the first pattern 220 and the second pattern 230 may be alternately spaced apart from each other on the first active material layer 210.
  • an uneven shape may be formed on the first active material layer by the first pattern and the second pattern.
  • the amount of the impregnated electrolyte is remarkably reduced toward the current collector surface near the electrode surface, so that insertion and desorption of lithium ions is not smooth.
  • the problem that the charge-discharge performance is lowered.
  • the contact area between the positive electrode and the electrolyte can be increased, the electrolyte impregnation property can be improved, the charge and discharge performance of the battery This can be improved.
  • the electrolyte may be easily penetrated in the direction of the current collector while the first loaded active material layer is exposed between the first pattern and the second pattern, thereby further improving the electrolyte impregnation property.
  • the thickness of the first pattern may be greater than the thickness of the second pattern.
  • the thickness of the first pattern may be 1.1 times to 2 times the thickness of the second pattern, and more specifically, may be 1.2 times to 1.5 times.
  • the volume expansion rate of the second pattern may be greater than the volume expansion rate of the first pattern.
  • the volume expansion rate may be calculated from an increase in thickness after one charge / discharge compared to the initial thickness of the first pattern or the second pattern. Specifically, the ratio of the amount of change in thickness increased after the first charge / discharge cycle with respect to the initial electrode thickness.
  • the first charge-discharge cycle proceeds with CC-CV charging to 0.1C, 4.25V to 4.4V, 0.02C cut off, and discharges to CC discharge with 0.1C, 3V cut off.
  • volume expansion ratio is calculated by Equation 1 below, where A is the thickness of the first pattern or the second pattern before charging and discharging, and B may be the thickness of the first pattern or the second pattern after charging and discharging. .
  • the thickness can be measured with a micrometer, a mouse, or through a scanning electron microscope.
  • the thickness of the second pattern is relatively small even by the large volume expansion of the second pattern whose thickness is relatively small, the thickness of the anode may not be excessively increased, and even if it is not in contact with or is adjacent to the neighboring first pattern. Excessive stress may not be applied to the first pattern. Therefore, excessive increase in battery thickness due to positive electrode expansion during charging can be prevented, and mechanical stability of the positive electrode can be secured.
  • the first active material layer may include first active material particles
  • the first pattern may include the first pattern active material particles
  • the second pattern may include the second pattern active material particles.
  • composition of at least one of the first active material particles, the first pattern active material particles, and the second pattern active material particles may be different from the remaining composition.
  • the first active material particles and the first pattern active material particles are LiCoO 2
  • the second pattern active material particles are LiNi 1 -x1- y1 Co x1 Mn y1 O 2 (0 ⁇ x1 ⁇ 1 and may be at least any one of 0 ⁇ y1 ⁇ 1) and LiNi 1 -x2- y2 Co x2 Al y2 O 2 (0 ⁇ x2 ⁇ 1 , and 0 ⁇ y2 ⁇ 1).
  • the LiNi 1 -x1- y1 Co x1 Mn y1 O 2 (0 ⁇ x1 ⁇ 1 and 0 ⁇ y1 ⁇ 1) is LiNi 0. 6 Co 0 . 2 Mn 0 . May be 2 O 2
  • LiNi 1-x2-y2 Co x2 Al y2 O 2 (0 ⁇ x2 ⁇ 1 and 0 ⁇ y2 ⁇ 1) may be LiNi 0.85 Co 0.1 Al 0.05 O 2 .
  • LiCoO 2 When LiCoO 2 is used as the first active material particles and the first pattern active material particles included in the first active material layer and the first pattern, which occupy most of the components disposed on the current collector, when driven at a high voltage based on the characteristics of LiCoO 2 High capacity of the cell can be achieved.
  • LiCoO 2 In use, since the manufacturing, coating, and rolling process is easy, there is an advantage that the manufacturing cost and time can be reduced and the electrode density can be increased.
  • the second pattern electrode active material particles including the second pattern located on the electrode LiNi 1 -x1- y1 Co x1 Mn y1 O 2 (0 ⁇ x1 ⁇ 1 and 0 ⁇ y1 ⁇ 1) and LiNi 1 -x2 - y2 Co x2 Al y2 O 2 (0 ⁇ x2 ⁇ 1 , and 0 ⁇ y2 ⁇ 1) at least by using any of the insertion of lithium, and tally the seamless LiNi 1 -x1- y1 Co x1 Mn y1 O 2 (0 ⁇ x1 ⁇ 1 and 0 ⁇ y1 ⁇ 1) and LiNi 1 -x2- y2 Co x2 Al y2 O 2 (0 ⁇ x2 ⁇ 1 , and 0, the charge and discharge characteristics of the battery gihayeo on the nature of ⁇ y2 ⁇ 1) may be improved have.
  • LiNi 1- x1- y1 Co x1 Mn y1 O 2 (0 ⁇ x1 ⁇ 1 and 0 ⁇ y1 ⁇ 1)
  • LiNi 1- x2- y2 Co x2 Al y2 O 2 (0 ⁇ x2 ⁇ 1 and 0 ⁇ y2 ⁇ 1)
  • the thickness of the second pattern during charge and discharge may be It can be prevented from becoming excessively larger than the thickness.
  • the thickness of the anode may not be excessively increased, and the first pattern may not be in contact with the neighboring first pattern, or excessive stress may not be applied to the first pattern. Therefore, the increase in the size of the battery can be prevented, and the mechanical stability of the positive electrode can be ensured. The effect may be further improved by alternately arranging the first pattern and the second pattern.
  • the first active material particles is LiNi 1 -x1- y1 Co x1 Mn y1 O 2 (1 0 ⁇ x1 ⁇ 1 and 0 ⁇ y1 ⁇ ) and LiNi 1- x2- y2 Co x2 Al y2 O 2 (0 ⁇ x2 ⁇ 1 and 0 ⁇ y2 ⁇ 1), wherein the first pattern active material particles and the second pattern active material particles are LiCoO 2 .
  • the difference in porosity of the second pattern is smaller than that of the first pattern.
  • the LiNi 1 -x1- y1 Co x1 Mn y1 O 2 (0 ⁇ x1 ⁇ 1 and 0 ⁇ y1 ⁇ 1) is LiNi 0. 6 Co 0 . 2 Mn 0 . May be 2 O 2 .
  • LiNi 1 -x2- y2 Co x2 Al y2 O 2 (0 ⁇ x2 ⁇ 1 , and 0 ⁇ y2 ⁇ 1) may be LiNi 0.85 Co 0.1 Al 0.05 O 2 .
  • a first active material particles included in the first active material layer which accounts for most of the configuration which is located on the collector LiNi 1 -x1- y1 Co x1 Mn y1 O 2 (0 ⁇ x1 ⁇ 1 and 0 ⁇ y1 ⁇ 1) and LiNi 1 -x2- y2 Co x2 Al y2 O 2 (0 ⁇ x2 ⁇ 1 , and 0 ⁇ y2 ⁇ 1) at least by the use of any one, the insertion of lithium, and tally the seamless LiNi 1 -x1- Co x1 y1 y1 Mn O 2 of (0 ⁇ x1 ⁇ 1 and 0 ⁇ y1 ⁇ 1) and LiNi 1 -x2- improved y2 Co x2 Al y2 O 2 ( 0 ⁇ x2 ⁇ 1 , and 0 ⁇ y2 ⁇ 1) charge-discharge characteristics of the battery to the characteristics of gihayeo In addition, a change in battery thickness during discharge may be minimized.
  • the first pattern active material particles and the second pattern active material particles it is possible to ensure a high capacity of the battery when driving a high voltage, the first pattern and the second pattern based on the LiCoO 2 characteristics that the manufacturing process is smooth May be smoothly formed.
  • the energy density may be improved by the second pattern, thereby improving the capacity of the battery.
  • the volume expansion rate of the second pattern may be greater than the volume expansion rate of the first pattern. Since the thickness of the second pattern is smaller than the thickness of the first pattern, even if a large volume expansion of the second pattern, the thickness of the second pattern may not exceed the thickness of the first pattern so that the thickness of the anode does not increase excessively.
  • the first pattern may not be in contact with the neighboring first pattern, or excessive stress may not be applied to the first pattern.
  • the porosity of the first pattern may be at least 5% greater than the porosity of the second pattern, more specifically, the porosity of the first pattern may be 23% to 30%, and the porosity of the second pattern is 18% to 25 May be%.
  • the porosity can be calculated by measuring the loading amount of the electrode (g / 25cm 2 ) and the electrode thickness.
  • the first active material particles are LiCoO 2
  • the first pattern active material particles are LiNi 1 -x1- y1 Co x1 Mn y1 O 2 (0 ⁇ x1 ⁇ 1 and 0 ⁇ y1 ⁇ 1) and a LiNi 1 -x2- y2 Co x2 Al y2 O 2 (0 ⁇ x2 ⁇ 1 , and 0 ⁇ y2 ⁇ least one of 1)
  • the second pattern electrode active material particles At least one of LiFePO 4 and LiMn 2 O 4 differs in that the porosity of the second pattern is smaller than that of the first pattern.
  • the LiNi 1 -x1- y1 Co x1 Mn y1 O 2 (0 ⁇ x1 ⁇ 1 and 0 ⁇ y1 ⁇ 1) is LiNi 0. 6 Co 0 . 2 Mn 0 . May be 2 O 2 .
  • LiNi 1-x2-y2 Co x2 Al y2 O 2 (0 ⁇ x2 ⁇ 1 and 0 ⁇ y2 ⁇ 1) may be LiNi 0.85 Co 0.1 Al 0.05 O 2 .
  • LiCoO 2 as the first active material particles included in the first active material layer, which occupies most of the components disposed on the current collector, a high capacity of the battery may be achieved when driven at a high voltage based on the characteristics of LiCoO 2 .
  • LiCoO 2 In use, since manufacturing, coating, and rolling processes are easy, manufacturing cost and time are reduced, and there is an advantage of increasing electrode density.
  • the first pattern active material particles included in the first pattern positioned on the electrode surface are LiNi 1- x 1- y 1 Co x 1 Mn y 1 O 2 (0 ⁇ x1 ⁇ 1 and 0 ⁇ y1 ⁇ 1) and LiNi 1- x2 - y2 Co x2 Al y2 O 2 (0 ⁇ x2 ⁇ 1 , and 0 ⁇ y2 ⁇ 1) at least by using any of the insertion of lithium, and tally the seamless LiNi 1 -x1- y1 Co x1 Mn y1 O 2 (0 ⁇ x1 ⁇ 1 and 0 ⁇ y1 ⁇ 1) and LiNi 1 -x2- y2 Co x2 Al y2 O 2 (0 ⁇ x2 ⁇ 1 , and 0, the charge and discharge characteristics of the battery gihayeo on the nature of ⁇ y2 ⁇ 1) may be improved have.
  • LiFePO 4 and LiMn 2 O 4 as the second pattern active material particles contained in the second pattern, LiFePO 4 Based on the strong binding force of the PO within, and the structural stability of the three-dimensional tunnel structure of LiMn 2 O 4 , the thermal stability of the battery can be secured.
  • the second pattern because the first electrode included in a small amount compared with the first pattern to a first pattern electrode active material particles in order to increase the charge and discharge characteristics LiNi 1 -x1- y1 Co x1 Mn y1 O 2 (0 ⁇ x1 ⁇ 1 and 0 ⁇ It is advantageous to use at least one of y1 ⁇ 1) and LiNi 1 - x2 -y2 Co x2 Al y2 O 2 (0 ⁇ x2 ⁇ 1 and 0 ⁇ y2 ⁇ 1).
  • the energy density may be improved by the second pattern, thereby improving the capacity of the battery.
  • the volume expansion rate of the second pattern may be greater than the volume expansion rate of the first pattern. Since the thickness of the second pattern is smaller than the thickness of the first pattern, the thickness of the second pattern may not exceed the thickness of the first pattern even by the large volume expansion of the second pattern so that the thickness of the electrode does not increase excessively.
  • the first pattern may not be in contact with the neighboring first pattern, or excessive stress may not be applied to the first pattern.
  • the porosity of the first pattern may be at least 5% greater than the porosity of the second pattern, more specifically, the porosity of the first pattern may be 23% to 30%, and the porosity of the second pattern is 18% to 25 May be%.
  • the porosity can be calculated by measuring the loading amount of the electrode (g / 25cm 2 ) and the electrode thickness.
  • the first active material layer, the first pattern, and the second pattern may each include a binder and a conductive material.
  • the binder may be polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride, polyacrylonitrile, polymethylmethacrylate, Polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, ethylene-propylene-diene monomer (EPDM), Various kinds of binder polymers such as 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 copolymers can be used. Can be.
  • PVDF-co-HFP polyvinylidene fluoride-hexafluoropropylene copolymer
  • SBR styrene but
  • 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 carbon black, 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 positive electrode according to the embodiments of the present invention may be prepared by applying a slurry made by mixing an electrode mixture including an active material, a conductive material, and a binder in a solvent on a current collector, followed by drying and rolling. Specifically, after the first active material layer is formed on the current collector by the above method, the first pattern and the second pattern may be formed on the first active material layer.
  • the first active material layer, the first pattern, and the second pattern may be used in combination with at least one of screen printing, inkjet, spray, gravure printing, thermal transfer, plate printing, intaglio printing, and offset printing. Can be.
  • the solvent may be a solvent generally used in the art, and may include dimethyl sulfoxide (DMSO), isopropyl alcohol, N-methylpyrrolidone (NMP), acetone or acetone. Water, and the like, one of these alone or a mixture of two or more thereof may be used.
  • DMSO dimethyl sulfoxide
  • NMP N-methylpyrrolidone
  • acetone or acetone. Water, and the like, one of these alone or a mixture of two or more thereof may be used.
  • the slurry for forming the first active material layer may be applied and dried on the current collector to form the first active material layer.
  • the pattern mask is disposed on the first active material layer, the slurry for forming the second pattern is applied and dried, and then rolled to selectively form a second pattern having a specific thickness on a portion of the first active material layer. have.
  • the pattern mask may be removed, and another pattern mask may be disposed on a part of the first active material layer and the second pattern to form the first pattern.
  • the slurry for forming the first pattern may be applied and dried, and then rolled to form a first pattern having a specific thickness.
  • the pattern mask may be removed.
  • the first pattern and the second pattern may be formed using an etching process.
  • the first active material particles, the binder, and the conductive material of the first active material layer may be included in a weight ratio of 95 to 99: 0.7 to 2.5: 0.3 to 2.5, and the first pattern active material particles, binder, and conductive material in the first pattern may be 95 to 99. It may be included in a weight ratio of 99: 0.7 to 2.5: 0.3 to 2.5, the second pattern active material particles, the binder and the conductive material in the second pattern may be included in a weight ratio of 95 to 99: 0.7 to 2.5: 0.3 to 2.5.
  • a secondary battery according to another embodiment of the present invention may include a negative electrode, a positive electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte, and the positive electrode may be an electrode according to an embodiment of the present invention.
  • the negative electrode may include a negative electrode current collector and a negative electrode active material layer disposed on the negative electrode current collector and including a negative electrode active material.
  • the negative electrode current collector is conductive without causing chemical change in the secondary battery, and is, for example, on the surface of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel. Surface treated with carbon, nickel, titanium, silver or the like can be used.
  • the negative electrode active material may be a compound capable of reversible intercalation and deintercalation of lithium.
  • 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 separator separates the negative electrode from the positive electrode and provides a passage for lithium ions, and can be used without particular limitation as long as the separator is used as a separator in a secondary battery. In particular, it has a low resistance to ion migration of the electrolyte and an excellent ability to hydrate the electrolyte. It is preferable.
  • 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.
  • 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 including 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.
  • the electrolyte may 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, but are not limited thereto.
  • the electrolyte may include a non-aqueous organic solvent and a metal salt.
  • non-aqueous organic solvent for example, N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butylo lactone, 1,2-dime Methoxy ethane, tetrahydroxy franc, 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolon, formamide, dimethylformamide, dioxoron, acetonitrile, nitromethane, methyl formate, Methyl acetate, phosphate triester, trimethoxy methane, dioxorone derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, ethers, pyrion
  • An aprotic organic solvent such as methyl acid or ethyl
  • ethylene carbonate and propylene carbonate which are cyclic carbonates among the carbonate-based organic solvents, may be preferably used as high-viscosity organic solvents because they have high dielectric constants to dissociate lithium salts well, such as dimethyl carbonate and diethyl carbonate.
  • high-viscosity organic solvents because they have high dielectric constants to dissociate lithium salts well, such as dimethyl carbonate and diethyl carbonate.
  • an electrolyte having a high electrical conductivity can be made, and thus it can be more preferably used.
  • the metal salt may be a lithium salt
  • the lithium salt is a material that is readily soluble in the non-aqueous electrolyte, for example, is in the lithium salt anion F -, Cl -, I - , NO 3 -, N (CN ) 2 -, BF 4 -, ClO 4 -, PF 6 -, (CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF - , (CF 3) 6 P - , CF 3 SO 3 -, CF 3 CF 2 SO 3 -, (CF 3 SO 2) 2 N -, (FSO 2) 2 N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2 ) 2 CH -, (SF 5) 3 C -, (CF 3 SO 2) 3 C -, CF 3 (CF 2) 7 SO 3 -, CF 3 CO 2 -, CH 3 CO 2 -
  • the electrolyte includes, for example, haloalkylene carbonate-based compounds such as difluoro ethylene carbonate, pyridine, tri, etc. for the purpose of improving battery life characteristics, reducing battery capacity, and improving discharge capacity of the battery.
  • haloalkylene carbonate-based compounds such as difluoro ethylene carbonate, pyridine, tri, etc.
  • Ethyl phosphite triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone, N, N-substituted imida
  • One or more additives such as zolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxy ethanol or aluminum trichloride may be included.
  • a battery module including the secondary battery as a unit cell and a battery pack including the same are provided. Since the battery module and the battery pack include the secondary battery having high capacity, high rate characteristics, and cycle characteristics, a medium-large device selected from the group consisting of an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, and a power storage system It can be used as a power source.
  • a mixture was prepared by mixing LiCoO 2 having an average particle diameter (D 50 ) of 16 ⁇ m, polyvinylidene fluoride (PVdF) as a binder, and carbon black as a conductive material at a weight ratio of 97: 1.8: 1.2. 28.9 g of N-methylpyrrolidone (NMP) was added to the mixture to prepare a positive electrode slurry.
  • the positive electrode slurry was applied and dried to an aluminum current collector having a thickness of 20 ⁇ m. At this time, the temperature of the air circulated was 120 ° C. Thereafter, rolling was performed to form a first active material layer having a thickness of 60 ⁇ m.
  • LiNi 0 having an average particle diameter (D 50 ) of the second pattern active material particles is 13 ⁇ m . 6 Co 0 . 2 Mn 0 . 5 g of a mixture was prepared by mixing 2 O 2 , PVdF as a binder, and carbon black as a conductive material at a weight ratio of 97: 1.8: 1.2. 28.9 g of NMP was added to the mixture to prepare a positive electrode slurry. On the other hand, after placing a pattern mask on a part of the first active material layer, the positive electrode slurry was applied and dried. At this time, the temperature of the air circulated was 120 ° C. Thereafter, the pattern mask was removed and rolled to form a second pattern having a thickness of 20 ⁇ m and a porosity of 24%.
  • a mixture was prepared by mixing LiCoO 2 having an average particle diameter (D 50 ) of the first pattern active material particles at 12 ⁇ m, PVdF of a binder, and carbon black of a conductive material at a weight ratio of 97: 1.8: 1.2. 28.9 g of NMP was added to the mixture to prepare a positive electrode slurry.
  • the positive electrode slurry was applied onto the first active material layer and then dried. At this time, the temperature of the air circulated was 120 ° C. Thereafter, the pattern mask was removed and rolled to form a first pattern having a thickness of 30 ⁇ m and a porosity of 29%.
  • the current collector on which the first active material layer, the first pattern, and the second pattern were formed was dried in a vacuum oven at 130 ° C. for 12 hours, and then punched into a circle of 1.4875 cm 2 to prepare a positive electrode.
  • a lithium metal thin film cut into a round shape of 1.7671 cm 2 was used as a negative electrode, and a battery was manufactured using the negative electrode and the prepared positive electrode.
  • an electrode assembly was prepared by placing a separator of porous polyethylene between the anode and the cathode. Meanwhile, vinylene carbonate (VC) dissolved at 0.5% by weight was dissolved in a mixed solution of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) at a volume of 7: 3, and LiPF 6 was dissolved (1 M concentration). An electrolyte solution was prepared. The electrolyte was injected into the electrode assembly to prepare a lithium coin half cell.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • Example 2 manufacture of a battery
  • LiNi 0 having an average particle diameter (D 50 ) of 13 ⁇ m as the first active material particles . 85 Co 0 . 1 Al 0 . A 05 O 2, a, except that the average particle diameter (D 50) is 14 ⁇ m of the LiCoO 2, the average particle diameter (D 50) to a second pattern electrode active material particle 14 ⁇ m of LiCoO 2 as a first pattern electrode active material particle is carried out
  • a positive electrode and a battery were manufactured in the same manner as in Example 1.
  • the thickness of the first active material layer was 50 ⁇ m.
  • the thickness of the first pattern was 35 ⁇ m and the porosity was 29%.
  • the thickness of the second pattern was 25 ⁇ m and the porosity was 24%.
  • LiCoO 2 having an average particle diameter (D 50 ) of 15 ⁇ m as the first active material particles, and LiNi 0. Having an average particle diameter (D 50 ) of 14 ⁇ m as the first pattern active material particles . 6 Co 0 . 2 Mn 0 . 2 for O 2, and is first to prepare a positive electrode and battery in the same manner as in Example 1 except that the average particle diameter (D 50) to the second pattern of the active material particles 5 ⁇ m LiFePO 4.
  • the thickness of the first active material layer was 70 ⁇ m.
  • the thickness of the first pattern was 24 ⁇ m and the porosity was 29%.
  • the thickness of the second pattern was 16 ⁇ m and the porosity was 24%.
  • a positive electrode and a battery were manufactured in the same manner as in Example 1, except that the thickness of the first pattern was 20 ⁇ m and the thickness of the second pattern was 30 ⁇ m.
  • Comparative example 2 manufacture of a battery
  • a positive electrode and a battery were manufactured in the same manner as in Example 2, except that the thickness of the first pattern was 25 ⁇ m and the thickness of the second pattern was 35 ⁇ m.
  • a positive electrode and a battery were manufactured in the same manner as in Example 3, except that the thickness of the first pattern was 16 ⁇ m and the thickness of the second pattern was 24 ⁇ m.
  • one cycle and two cycles were charged and discharged at 0.1C, and charging and discharging were performed at 0.5C from 3 cycles to 49 cycles.
  • the 50 cycles were finished in the state of charging (with lithium in the negative electrode) and the capacity retention rate was evaluated.
  • Discharge capacity (mAh / g) and initial efficiency (%) were derived through the result at the time of single charge / discharge. Specifically, the initial efficiency (%) was derived by the following calculation.
  • the capacity retention rate and the electrode thickness change rate were derived by the following calculations, respectively.
  • Capacity retention rate (%) (49 discharge capacity / 1 discharge capacity) ⁇ 100
  • the volume expansion ratio of the first pattern or the second pattern is calculated by Equation 1 below, where A is the thickness of the first pattern or the second pattern before charge and discharge, and B is the thickness of the first pattern or the second pattern after charge and discharge. to be.
  • the thickness was confirmed by micrometer.
  • the electrode thickness change rate is relatively small, and the discharge capacity and the capacity retention rate are relatively large in the case of Examples. You can check it. This is because the thickness of the second pattern having a relatively large volume expansion ratio is smaller than the thickness of the first pattern, and thus the anode thickness may be less changed when charging and discharging is repeated, and a portion of the first active material layer contacting with the electrolyte may be sufficiently secured. I think it is.

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Abstract

La présente invention concerne une électrode positive et une batterie secondaire la comprenant et, spécifiquement, une électrode positive et une batterie secondaire la comprenant, comportant : un collecteur de courant ; une première couche de matériau actif, qui comporte une première particule de matériau actif et qui est placée sur le collecteur de courant ; et un premier motif et un second motif, qui sont disposés en alternance sur la première couche de matériau actif tout en étant espacés l'un de l'autre, le premier motif comportant une première particule de matériau actif de motif, le second motif comportant une seconde particule de matériau actif de motif, le premier motif étant plus épais que le second motif, et le second motif présentant un taux d'expansion volumique supérieur à celui du premier motif.
PCT/KR2017/007116 2016-07-04 2017-07-04 Électrode positive et batterie secondaire la comprenant Ceased WO2018008954A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US15/751,343 US10622625B2 (en) 2016-07-04 2017-07-04 Positive electrode and secondary battery including the same
JP2018524381A JP6763549B2 (ja) 2016-07-04 2017-07-04 正極及び前記正極を含む二次電池
PL17824510T PL3316358T3 (pl) 2016-07-04 2017-07-04 Elektroda dodatnia i bateria akumulatorowa zawierająca tę elektrodę dodatnią
CN201780004011.9A CN108352506B (zh) 2016-07-04 2017-07-04 正极和包含该正极的二次电池
EP17824510.6A EP3316358B1 (fr) 2016-07-04 2017-07-04 Électrode positive et batterie secondaire la comprenant

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KR20160083958 2016-07-04
KR10-2016-0083958 2016-07-04
KR1020170085057A KR101948848B1 (ko) 2016-07-04 2017-07-04 양극 및 상기 양극을 포함하는 이차 전지
KR10-2017-0085057 2017-07-04

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CN113410424A (zh) * 2021-06-17 2021-09-17 昆山宝创新能源科技有限公司 一种锂化硅基负极极片及其制备方法和应用

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EP2498323A2 (fr) * 2011-03-09 2012-09-12 Samsung SDI Co., Ltd. Matériau actif positif et électrode et batterie au lithium le contenant
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US9012090B2 (en) * 2012-12-27 2015-04-21 Palo Alto Research Center Incorporated Advanced, high power and energy battery electrode manufactured by co-extrusion printing
KR20160050255A (ko) * 2014-10-29 2016-05-11 주식회사 엘지화학 다층 구조의 이차전지용 전극 및 이의 제조방법

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WO2007052803A1 (fr) * 2005-11-07 2007-05-10 Matsushita Electric Industrial Co., Ltd. Electrode pour une batterie rechargeable au lithium, ladite batterie et procede de fabrication de celle-ci
EP2498323A2 (fr) * 2011-03-09 2012-09-12 Samsung SDI Co., Ltd. Matériau actif positif et électrode et batterie au lithium le contenant
US9012090B2 (en) * 2012-12-27 2015-04-21 Palo Alto Research Center Incorporated Advanced, high power and energy battery electrode manufactured by co-extrusion printing
JP2014191876A (ja) * 2013-03-26 2014-10-06 Dainippon Screen Mfg Co Ltd リチウムイオン二次電池用電極、リチウムイオン二次電池、電池用電極製造装置および電池用電極製造方法
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019507460A (ja) * 2016-07-04 2019-03-14 エルジー・ケム・リミテッド 負極および前記負極を含む二次電池
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CN113410424A (zh) * 2021-06-17 2021-09-17 昆山宝创新能源科技有限公司 一种锂化硅基负极极片及其制备方法和应用

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