WO2024058462A1 - Composite de particules de matériau actif de liant, cathode le comprenant pour batterie secondaire au lithium, et procédé de préparation correspondant - Google Patents

Composite de particules de matériau actif de liant, cathode le comprenant pour batterie secondaire au lithium, et procédé de préparation correspondant Download PDF

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WO2024058462A1
WO2024058462A1 PCT/KR2023/012766 KR2023012766W WO2024058462A1 WO 2024058462 A1 WO2024058462 A1 WO 2024058462A1 KR 2023012766 W KR2023012766 W KR 2023012766W WO 2024058462 A1 WO2024058462 A1 WO 2024058462A1
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binder
active material
material particle
positive electrode
solvent
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English (en)
Korean (ko)
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김찬훈
강지수
이정은
윤기로
홍영선
강병수
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한국생산기술연구원
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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
    • H01M4/36—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
    • 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
    • H01M4/04—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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0419—Methods of deposition of the material involving spraying
    • 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
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 binder-active material particle composite, a positive electrode for a lithium secondary battery containing the same, and a method for manufacturing the same.
  • Secondary batteries are an energy source that can be reused through charging, and are used as large-capacity power storage batteries such as electric vehicles and ESS (Energy Storage Systems) and small-sized energy sources in electronic devices such as mobile phones, laptops, and vacuum cleaners.
  • ESS Electronic Storage Systems
  • the secondary battery market has expanded rapidly with the development of electric vehicle technology, and in order to respond to the increased carbon tax and CO2 emissions management as environmental issues have recently emerged, the direction is to lower carbon emissions throughout the entire process of secondary battery production, use, and disposal. It is being demanded.
  • the currently used lithium secondary battery positive electrode manufacturing process is a wet electrode process, which requires a drying process of the organic solvent used to dissolve the polymer binder, and this process consumes considerable energy and time.
  • NMP N-Methylpyrrolidone
  • NMP N-Methylpyrrolidone
  • the energy used to dry it accounts for 40% of the entire cell manufacturing process.
  • Korea a renewable energy-poor country, processes that consume a lot of energy generate a lot of CO 2 , so improving the energy efficiency of the secondary battery process is essential for improving the performance of secondary batteries and making them low-carbon.
  • the purpose of the present invention is to solve the above problems, and to provide a lithium secondary battery electrode drying process that can save a lot of energy by omitting the slurry drying process, which is a process that consumes a lot of energy among the existing lithium secondary battery electrode processes. there is.
  • the aim is to provide a binder-active material particle complex that can be used in a dry process and can dramatically improve the electrical conductivity of the surface of the active material by strengthening the adhesion between positive electrode active material particles and allowing the conductive material to directly contact the surface of the positive active material.
  • the goal is to provide a positive electrode for lithium secondary batteries that can be manufactured through a dry process and has excellent lifespan characteristics when used in lithium secondary batteries.
  • the shell 200 may have a network shape formed of fibers containing the binder.
  • the pore diameter of the shell 200 may be 0.05 to 2 ⁇ m.
  • the binder is polyvinylidene fluoride (PVdF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP), polyvinylidene fluoride-tetrafluoroethylene copolymer (PVdF-TFE) ), polyvinyl pyrrolidinone, polyethyleneoxide, polyethyleneglycol, polyacrylonitrile, polyvinylchloride, polymethylmethacrylate, polypropylene It may include one or more selected from the group consisting of polypropyleneoxide, polydimethylsiloxane, polyvinylidenecarbonate, nitrile butadiene rubber (NBR), and combinations thereof.
  • PVdF polyvinylidene fluoride
  • PVdF-HFP polyvinylidene fluoride-hexafluoropropylene copolymer
  • PVdF-TFE polyvinylidene fluoride-tetrafluor
  • the binder is polyvinylidene fluoride (PVdF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP), polyvinylidene fluoride-tetrafluoroethylene copolymer (PVdF-TFE) ) and combinations thereof.
  • PVdF polyvinylidene fluoride
  • PVdF-HFP polyvinylidene fluoride-hexafluoropropylene copolymer
  • PVdF-TFE polyvinylidene fluoride-tetrafluoroethylene copolymer
  • the positive electrode active material may be in the form of granules.
  • the size of the positive electrode active material may be 1 to 20 ⁇ m.
  • the positive electrode active material is lithium nickel cobalt manganese oxide (NCM), lithium iron phosphate (LiFePO 4 ), lithium nickel cobalt aluminum oxide (NCA), lithium cobalt oxide (LiCoO 2 ), lithium It may include one or more types selected from the group consisting of nickel-based oxide (LiNiO 2 ) and lithium manganese-based oxide (LiMn 2 O 4 ).
  • lithium nickel cobalt manganese oxide may be represented by structural formula 1 below.
  • x is 0.6 ⁇ x ⁇ 0.95
  • y is 0.01 ⁇ y ⁇ 0.2
  • z is 0.01 ⁇ z ⁇ 0.2.
  • the binder-active material particle composite further includes a conductive material located in the pores, and the conductive material contacts and connects with the positive electrode active material particles of the core and the positive active material particles of other cores adjacent to the core, respectively. You can.
  • the conductive material may include one or more selected from the group consisting of carbon black, acetylene black, Ketjen black, carbon fiber, carbon nanotube, graphene, and Denka black.
  • the binder-active material particle composite may include 100 parts by weight of the positive electrode active material; 1 to 20 parts by weight of the binder; and 1 to 20 parts by weight of the conductive material.
  • a positive electrode including the binder-active material particle complex; cathode; A lithium secondary battery including an electrolyte is provided.
  • NIPS nonsolvent induced phase separation
  • the mixed solution may include 0.5 to 2 parts by weight of the binder based on 100 parts by weight of the solvent.
  • the solvent may include one or more selected from the group consisting of dimethyl sulfoxide (DMSO), dimethylacetamide (DMAC), and dimethylformamide (DMF).
  • DMSO dimethyl sulfoxide
  • DMAC dimethylacetamide
  • DMF dimethylformamide
  • the non-solvent may be 300 to 2,000 parts by weight based on 100 parts by weight of the mixed solution.
  • the non-solvent may include one or more selected from the group consisting of water, ethanol, n-propanol, iso-propanol, hexane, and n-hexane.
  • a method for manufacturing a positive electrode for a lithium secondary battery is provided.
  • step (4) may be performed as a dry process.
  • the electrostatic spraying may be performed at a voltage of 5 to 30 V.
  • the rolling may be performed using a roll press heated to 20 to 150° C. and at a speed of 1 to 20 mm/s.
  • the binder-active material particle composite of the present invention strengthens the adhesion between active material particles by forming a binder coated on the surface of the positive electrode active material into a porous shell shape and allows the conductive material to directly contact the surface of the positive active material, thereby dramatically improving the electrical conductivity of the surface of the active material. You can do it.
  • the positive electrode for lithium secondary batteries containing the binder-active material particle composite of the present invention can be manufactured through a dry process, so the slurry drying process, which is a process that consumes a lot of energy among the existing lithium secondary battery electrode processes, can be omitted, thereby saving a lot of energy. You can save.
  • a lithium secondary battery including a positive electrode for a lithium secondary battery including the binder-active material particle composite of the present invention has excellent lifespan characteristics.
  • FIG. 1 is a schematic diagram of a binder-active material particle composite according to one embodiment of the present invention.
  • Figure 2 is a schematic diagram showing the process of manufacturing a binder-active material particle composite according to one embodiment of the present invention.
  • Figure 3 is a schematic diagram showing the process of manufacturing a positive electrode for a lithium secondary battery according to one embodiment of the present invention.
  • Figure 5 shows the first cycle results of Device Example 1 and Device Comparative Example 1 at a current density of 0.1 C.
  • Figure 6 shows the life characteristics results of Device Example 1 and Device Comparative Example 1 at a current density of 1 C.
  • first, second, etc. which will be used below, may be used to describe various components, but the components are not limited by the terms. The above terms are used only for the purpose of distinguishing one component from another.
  • a first component may be named a second component, and similarly, the second component may also be named a first component without departing from the scope of the present invention.
  • a component when referred to as being “formed” or “laminated” on another component, it may be formed or laminated directly on the entire surface or one side of the surface of the other component, but may also mean that the component is “formed” or “laminated” on another component. It should be understood that other components may exist.
  • the binder-active material particle composite the positive electrode for a lithium secondary battery containing the same, and the manufacturing method thereof will be described in detail.
  • this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims to be described later.
  • FIG. 1 is a schematic diagram of a binder-active material particle composite according to one embodiment of the present invention.
  • the present invention includes a core 100 containing positive electrode active material particles; and a shell 200 located on the core 100, including a binder, binding the core and other neighboring cores together, and having pores formed therein.
  • the shell 200 may have a network shape formed of fibers containing the binder.
  • the pore diameter of the shell 200 may be 0.05 to 2 ⁇ m. If the pore diameter is 0.05 ⁇ m, it is undesirable because it is difficult for the conductive material to directly contact the surface of the active material particle. If it exceeds 2 ⁇ m, the adhesion between the binder and the active material particle may be excessively low, which is undesirable.
  • the binder is polyvinylidene fluoride (PVdF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP), polyvinylidene fluoride-tetrafluoroethylene copolymer (PVdF-TFE) ), polyvinyl pyrrolidinone, polyethyleneoxide, polyethyleneglycol, polyacrylonitrile, polyvinylchloride, polymethylmethacrylate, polypropylene It may include at least one selected from the group consisting of polypropyleneoxide, polydimethylsiloxane, polyvinylidenecarbonate, nitrile butadiene rubber (NBR), and combinations thereof, and preferably is polyvinylidene fluoride (PVdF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP), polyvinylidene fluoride-tetrafluor
  • the positive electrode active material may be in the form of granules.
  • the size of the positive electrode active material may be 1 to 20 ⁇ m, preferably 3 to 10 ⁇ m. If the size of the positive active material is less than 3 ⁇ m, it is undesirable because the overall surface area increases and a larger amount of binder is needed to maintain adhesion, and if it exceeds 10 ⁇ m, it is undesirable because it is difficult to form a uniform electrode. don't do it
  • the positive electrode active material is lithium nickel cobalt manganese oxide (NCM), lithium iron phosphate (LiFePO 4 ), lithium nickel cobalt aluminum oxide (NCA), lithium cobalt oxide (LiCoO 2 ), lithium It may include one or more types selected from the group consisting of nickel-based oxide (LiNiO 2 ) and lithium manganese-based oxide (LiMn 2 O 4 ).
  • lithium nickel cobalt manganese oxide may be represented by structural formula 1 below.
  • x is 0.6 ⁇ x ⁇ 0.95
  • y is 0.01 ⁇ y ⁇ 0.2
  • z is 0.01 ⁇ z ⁇ 0.2.
  • the binder-active material particle composite further includes a conductive material located in the pores, and the conductive material contacts and connects with the positive electrode active material particles of the core and the positive active material particles of other cores adjacent to the core, respectively. You can.
  • the conductive material may include one or more selected from the group consisting of carbon black, acetylene black, Ketjen black, carbon fiber, carbon nanotube, graphene, and Denka black, and may preferably include carbon black. .
  • the binder-active material particle composite may include 1 to 20 parts by weight of the binder, preferably 2 to 10 parts by weight, based on 100 parts by weight of the positive electrode active material. If the binder is less than 2 parts by weight, it is not desirable because it cannot provide sufficient adhesion between active material particles, and if it is more than 20 parts by weight, the energy density of the electrode may be excessively low, which is undesirable.
  • the binder-active material particle composite may include 1 to 20 parts by weight of the conductive material, preferably 3 to 10 parts by weight, based on 100 parts by weight of the positive electrode active material. If the conductive material is less than 1 part by weight, it is undesirable because it is difficult to secure sufficient electrical conductivity of the electrode, and if it exceeds 20 parts by weight, the energy density of the electrode may be excessively low, which is undesirable.
  • the present invention provides a positive electrode comprising the binder-active material particle composite; cathode; It provides a lithium secondary battery including; and an electrolyte.
  • Figure 2 is a schematic diagram showing the process of manufacturing a binder-active material particle composite according to one embodiment of the present invention.
  • the present invention includes the steps of (a) mixing a positive electrode active material, a binder, and a solvent to prepare a mixed solution; and (b) adding the mixed solution to a non-solvent to induce nonsolvent induced phase separation (NIPS) to prepare a binder-active material particle composite, wherein the solvent dissolves the binder and , wherein the non-solvent does not dissolve the binder, providing a method for producing a binder-active material particle composite.
  • NIPS nonsolvent induced phase separation
  • the mixed solution may include 0.5 to 2 parts by weight of the binder based on 100 parts by weight of the solvent. If the binder is less than 0.5 parts by weight, it is undesirable because the binder may not be uniformly coated on the surface of the active material. If it exceeds 2 parts by weight, agglomeration between active material particles may occur, which is undesirable.
  • the solvent may include one or more selected from the group consisting of dimethyl sulfoxide (DMSO), dimethylacetamide (DMAC), and dimethylformamide (DMF), and preferably includes dimethyl sulfoxide. .
  • DMSO dimethyl sulfoxide
  • DMAC dimethylacetamide
  • DMF dimethylformamide
  • the non-solvent may contain 300 to 2,000 parts by weight, preferably 500 to 1,500 parts by weight, and more preferably 800 to 1,200 parts by weight, based on 100 parts by weight of the mixed solution. If the non-solvent is less than 300 parts by weight, solvent-non-solvent exchange does not occur sufficiently, making it difficult to form a porous shell containing a binder on the surface of the positive electrode active material, which is undesirable, and if it exceeds 2,000 parts by weight, the concentration during electrostatic spraying is low, so it is difficult to form a porous shell containing a binder on the surface of the positive electrode active material. This is undesirable because it takes a long time and is inefficient.
  • the non-solvent may include one or more selected from the group consisting of water, ethanol, n-propanol, iso-propanol, hexane, and n-hexane, and preferably includes water and ethanol.
  • Figure 3 is a schematic diagram showing the process of manufacturing a positive electrode for a lithium secondary battery according to an embodiment of the present invention.
  • the present invention includes the steps of (1) mixing a positive electrode active material, a binder, and a solvent to prepare a mixed solution; (2) adding the mixed solution to a non-solvent to prepare a first mixture including a binder-active material particle complex through non-solvent induced phase separation; (3) preparing a second mixture by dispersing a conductive material in the first mixture; (4) coating the second mixture on a current collector by electrostatic spraying; and (5) manufacturing a positive electrode by rolling the current collector coated with the second mixture.
  • step (4) may be performed as a dry process.
  • the electrostatic spraying may be performed at a voltage of 5 to 30 V. If the electrostatic spraying is performed at a voltage of less than 5 V, it is undesirable because residual solvent may exist in the current collector, and if the electrostatic spraying is performed at a voltage of less than 30 V, it is undesirable because it may become difficult to maintain a stable spray speed during electrostatic spraying.
  • the rolling may be performed using a roll press heated to 20 to 150°C. If the rolling is performed using a roll press heated to less than 20°C, it is undesirable because residual solvent may exist in the current collector, and if it exceeds 150°C, it is undesirable because the binder may deteriorate.
  • the rolling may be performed at a speed of 1 to 20 mm/s. If the rolling is performed at a speed of less than 1 mm/s, it is undesirable because it takes too much time to form the electrode and is inefficient, and if it exceeds 20 mm/s, it is undesirable because defects in the electrode may occur.
  • FIG. 2 is a schematic diagram showing the process of manufacturing a binder-active material particle composite according to one embodiment of the present invention. Referring to FIG. 2, the binder-active material particle composite of Example 1 was prepared.
  • a mixed solution was prepared by adding polyvinylidene fluoride (PVdF) binder and NCM-based positive electrode active material (Li(Ni 8 Co 1 Mn 1 )O 2 ) to dimethyl sulfoxide (DMSO) solvent. At this time, the concentration of the binder in the mixed solution was adjusted to 0.7 wt%, and 5 parts by weight of the binder was added based on 100 parts by weight of the active material particles.
  • PVdF polyvinylidene fluoride
  • DMSO dimethyl sulfoxide
  • a non-solvent mixed with distilled water and ethanol in a 1:1 volume ratio was added to the mixed solution.
  • the non-solvent was adjusted to 1,000 parts by weight based on 100 parts by weight of the mixed solution.
  • the mixture was stirred at 300 rpm for 5 minutes to prepare a binder-active material particle complex through non-solvent induced phase transition.
  • Figure 3 is a schematic diagram showing the process of manufacturing a positive electrode for a lithium secondary battery according to one embodiment of the present invention. Referring to FIG. 3, a positive electrode for a lithium secondary battery used in the lithium secondary battery cell of Device Example 1 was manufactured.
  • the conductive material (super P conductive carbon black) in ethanol
  • the binder-active material particle complex including solvent, non-solvent, and binder-active material particle complex
  • the conductive material was adjusted to contain 5 parts by weight based on 100 parts by weight of the active material particles.
  • the second mixture was coated on an aluminum (Al) current collector through electrostatic spraying. Electrostatic spraying was performed with one nozzle of 19 G and a voltage of 24 V. Afterwards, rolling was performed using a roll press heated to 150°C without a drying process, and a positive electrode for a lithium secondary battery having an electrode density of 5 mg cm -2 was finally manufactured without a separate drying process.
  • NCM-based positive electrode active material Li(Ni 8 Co 1 Mn 1 )O 2 particles as the positive electrode active material
  • 90 wt% of positive electrode active material 5 wt% of polyvinylidene fluoride (PVdF) binder
  • conductive material super P
  • a positive electrode was manufactured by mixing 5 wt% of conductive carbon black, slurry coating it on an aluminum foil (Al current collector) substrate, drying and rolling it, and then punching it to a certain size.
  • a 2032R Coin cell was manufactured using Comparative Example 1 as the anode, a PP separator, electrolyte (1.2 M LiPF6 in EC-EMC (EC:EMC, 3:7 by vol%) and 2 wt% VC), and a lithium metal anode.
  • a lithium secondary battery cell was manufactured.
  • Test Example 1 Confirmation of manufacture of binder-active material particle composite
  • Example 1 a core containing positive electrode active material particles and a network-shaped shell formed of fibers containing a binder on the core were formed. Additionally, it can be confirmed that the positive electrode active material is in the shape of granules.
  • Figure 5 shows the first cycle results of Device Example 1 and Device Comparative Example 1 at a current density of 0.1 C.
  • Figure 5 shows the voltage when the lithium secondary battery cell manufactured according to Device Example 1 and Device Comparative Example 1 was charged and discharged at a voltage range of 2.7 to 4.3 V and an applied current of 0.1 C (20 mAh g -1 ). This indicates capacity.
  • Figure 6 shows the life characteristics results of Device Example 1 and Device Comparative Example 1 at a current density of 1 C.
  • Figure 6 shows the voltage when the lithium secondary battery cell manufactured according to Device Example 1 and Device Comparative Example 1 was charged and discharged at a voltage range of 2.7 to 4.3 V and an applied current of 1 C (20 mAh g -1 ). This indicates capacity.
  • the lithium secondary battery cell manufactured according to Device Example 1 maintains a high reversible capacity equivalent to 92.5% of the reversible capacity of the lithium secondary battery manufactured according to Device Comparative Example 1 made by a wet process even after 300 cycles. It can be confirmed that the battery characteristics are similar to the performance level of cells manufactured using the existing wet process only through the dry process, which does not require a drying process because it does not use NMP.

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Abstract

L'invention concerne un composite de particules de matériau actif de liant, une cathode le comprenant pour une batterie secondaire au lithium, et un procédé de préparation correspondant. Le composite de particules actives de liant comprend : un noyau (100) contenant une particule de matériau actif de cathode ; et une enveloppe (200) disposée sur le noyau (100) et ayant des pores, l'enveloppe contenant un liant pour permettre au noyau et à un autre noyau adjacent d'adhérer l'un à l'autre, de telle sorte que le composite de particules actives de liant peut améliorer la force d'adhérence entre les matériaux actifs de cathode et amener un matériau conducteur en contact direct avec la surface du matériau actif de cathode, conduisant à une amélioration significative de la conductivité électrique de surface du matériau actif.
PCT/KR2023/012766 2022-09-15 2023-08-29 Composite de particules de matériau actif de liant, cathode le comprenant pour batterie secondaire au lithium, et procédé de préparation correspondant WO2024058462A1 (fr)

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KR10-2022-0116589 2022-09-15
KR1020220116589A KR20240037721A (ko) 2022-09-15 2022-09-15 바인더-활물질 입자 복합체, 그를 포함하는 리튬이차전지용 양극 및 그의 제조방법

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* Cited by examiner, † Cited by third party
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WO2000052774A1 (fr) * 1999-03-04 2000-09-08 Japan Storage Battery Co., Ltd. Materiau composite actif et leur procede de preparation, electrode et son procede de preparation, et cellule electrolytique non aqueuse
KR20150100028A (ko) * 2014-02-24 2015-09-02 (주)오렌지파워 이차 전지용 전극 조성물 및 이의 제조 방법
KR20160069385A (ko) * 2014-12-08 2016-06-16 주식회사 엘지화학 전극 복합체, 이를 포함하는 전기화학 소자 및 상기 전극 복합체의 제조방법
KR20180001519A (ko) * 2016-06-27 2018-01-04 주식회사 네패스 리튬이차전지용 음극의 제조 방법
KR20180087668A (ko) * 2017-01-25 2018-08-02 한양대학교 산학협력단 리튬 이차전지 복합전극용 슬러리 조성물, 이를 이용한 복합전극 제조방법 및 이를 포함하는 리튬 이차전지 제조방법.
KR20210123480A (ko) * 2020-04-03 2021-10-14 주식회사 엘지에너지솔루션 이차전지용 음극 및 이를 포함하는 이차전지
JP2022058020A (ja) * 2020-09-30 2022-04-11 国立研究開発法人産業技術総合研究所 全固体ナトリウム蓄電池に用いられる電極合材の製造方法、およびこれを用いた全固体ナトリウム蓄電池の製造方法

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