WO2018044112A2 - Procédé de fabrication d'électrode pour accumulateur au lithium et électrode pour accumulateur au lithium ainsi fabriquée - Google Patents

Procédé de fabrication d'électrode pour accumulateur au lithium et électrode pour accumulateur au lithium ainsi fabriquée Download PDF

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WO2018044112A2
WO2018044112A2 PCT/KR2017/009586 KR2017009586W WO2018044112A2 WO 2018044112 A2 WO2018044112 A2 WO 2018044112A2 KR 2017009586 W KR2017009586 W KR 2017009586W WO 2018044112 A2 WO2018044112 A2 WO 2018044112A2
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Prior art keywords
electrode
secondary battery
lithium secondary
primer layer
manufacturing
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PCT/KR2017/009586
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English (en)
Korean (ko)
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WO2018044112A3 (fr
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윤현웅
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주식회사 엘지화학
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Priority claimed from KR1020170111351A external-priority patent/KR102207524B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP17847037.3A priority Critical patent/EP3401984B1/fr
Priority to US16/076,433 priority patent/US10930967B2/en
Priority to CN201780013803.2A priority patent/CN108701817B/zh
Publication of WO2018044112A2 publication Critical patent/WO2018044112A2/fr
Publication of WO2018044112A3 publication Critical patent/WO2018044112A3/fr

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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
    • H01M4/139—Processes of manufacture
    • 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
    • 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 method for manufacturing an electrode for a lithium secondary battery which can prevent the separation phenomenon of the electrode active material and at the same time improve the performance and life characteristics of the lithium secondary battery, and a lithium secondary battery electrode manufactured therefrom.
  • lithium secondary batteries with high energy density and operating potential, long cycle life, and low self-discharge rate Batteries have been commercialized and widely used.
  • EVs electric vehicles
  • HEVs hybrid electric vehicles
  • Ni-MH secondary batteries are mainly used as power sources of such electric vehicles (EVs) and hybrid electric vehicles (HEVs).
  • lithium secondary batteries of high energy density, high discharge voltage and output stability are used. Research is actively underway and some are commercialized.
  • the lithium secondary battery has a structure in which a non-aqueous electrolyte containing lithium salt is impregnated in an electrode assembly having a porous separator interposed between a positive electrode and a negative electrode on which an active material is coated on an electrode current collector.
  • charging and discharging proceed while repeating a process of intercalation / deintercalation of lithium ions of a positive electrode to a negative electrode.
  • the capacity of the lithium secondary battery varies depending on the type of the electrode active material, the charge and discharge capacity is lowered as the cycle progresses. This phenomenon is most likely to prevent the active material from performing its function due to the increase in internal resistance due to separation between the active material or between the active material and the current collector due to the volume change of the electrode generated as the charge and discharge of the lithium secondary battery proceeds.
  • the lithium ions absorbed in the negative electrode do not escape properly, thereby reducing the active point of the negative electrode.
  • the charge and discharge capacity and life characteristics of the lithium secondary battery may decrease as the cycle progresses. .
  • the adhesion between the active material or the active material and the current collector may be insufficient, and thus may be peeled off from the current collector.
  • the content of the binder is increased, the resistance of the electrode is increased and the capacity and conductivity of the electrode are deteriorated.
  • the Republic of Korea Patent Publication No. 2016-0041299 can improve the adhesion and conductivity with the electrode mixture by using a current collector having a conductive adhesive portion coated on the surface with an area of 20 to 50% of the area of one surface of the current collector. It is disclosed.
  • Korean Patent Publication No. 2016-0040830 discloses a glass transition temperature (T g ) in which a primer layer and an electrode mixture layer are different in a multilayer structure electrode including a primer layer between a current collector and an electrode mixture layer including an electrode active material. It is disclosed that the adhesive can improve the adhesion between the current collector interface and the active material even in the case of a high-loading electrode by using a binder.
  • T g glass transition temperature
  • the present inventors have conducted various studies to solve the above problems, and as a result, the binding force between the current collector and the electrode layer is improved by introducing a patterned primer layer to increase the contact area.
  • an object of the present invention is to form a concave pattern of nanometer size by irradiating an ion beam on the surface of the primer layer provided between the current collector and the electrode layer.
  • Another object of the present invention to provide an electrode for a lithium secondary battery manufactured by the above manufacturing method.
  • It provides a method for manufacturing a lithium secondary battery electrode comprising the step of forming an electrode layer containing an electrode active material on the patterned primer layer.
  • the ion beam is characterized in that it comprises one or more selected from the group consisting of argon, oxygen, nitrogen, acetic acid, methane, carbon tetrafluoride, silane, ammonia and trimethylaluminum.
  • the ion beam is 1 to 500 keV energy, characterized in that for 1 second to 60 minutes to irradiate.
  • the thickness of the patterned primer layer is characterized in that 0.1 to 10 ⁇ m.
  • the ratio of the thickness of the patterned primer layer and the maximum depth of the concave pattern is 1: 0.01 to 1: 0.90.
  • the width of the concave pattern is 1 to 1000 nm
  • the pitch of the concave pattern is characterized in that 0.5 to 800 nm.
  • the conductive material may be natural graphite, artificial graphite, graphene, carbon black, denka black, acetylene black, ketjen black, super-P, channel black, furnace black, lamp black, summer black, carbon nanotube, graphite nanofiber, carbon It is characterized by one or more selected from the group consisting of nanofibers, aluminum, nickel, zinc oxide, potassium titanate, titanium oxide and polyphenylene derivatives.
  • the patterned primer layer is characterized in that it further comprises a binder.
  • the electrode is characterized in that the anode or the cathode.
  • the present invention provides an electrode for a lithium secondary battery manufactured by the above-described manufacturing method is located between the current collector and the electrode layer patterned primer layer.
  • the lithium secondary battery electrode manufactured by the method for manufacturing a lithium secondary battery electrode according to the present invention can easily form a concave pattern of the nanometer level by irradiating an ion beam on the surface of the primer layer.
  • the lithium secondary battery electrode manufactured by the manufacturing method increases the binding force of the electrode layer including the electrode active material to the current collector by the patterned primer layer having the concave pattern formed on the surface thereof, which prevents the electrode active material from peeling off. Structural stability and electrical conductivity can be improved. In addition, the capacity characteristics and cycle characteristics of the lithium secondary battery including the electrode may be improved.
  • FIG. 1 is a schematic diagram showing a cross-sectional structure of an electrode for a lithium secondary battery manufactured according to an embodiment of the present invention.
  • lithium secondary batteries As the field of application of lithium secondary batteries extends from mobile phones and wireless electronic devices to electric trains, the demand for high capacity and high stability lithium secondary batteries is increasing.
  • silicon having high theoretical capacity (4,200 mAh / g) and lithium metal (3,860 mAh / g) are used as the negative electrode active material or the loading amount of the electrode active material is increased.
  • the volume change of the active material due to charging and discharging is very large, such as 300%, or the adhesion of the active material is inadequate, resulting in the separation from the current collector, which negatively affects the capacity and life characteristics of the battery.
  • precipitates are formed on the surface to increase the physical and chemical instability of the lithium secondary battery.
  • the amount of the electrode active material is increased, the content of the binder included for the aggregation of the electrode active materials and the coating on the current collector also increases proportionally. The use of such an excess binder increases the resistance of the electrode and lowers the conductivity, thereby lowering the battery capacity.
  • due to the volume change during repeated charging and discharging may be peeled off with the current collector.
  • a lithium secondary battery electrode forming a concave pattern on the surface of the primer layer introduced between the current collector and the electrode active material through an ion beam. It provides a method of manufacturing.
  • the method for manufacturing an electrode for a lithium secondary battery includes the steps of forming a primer layer including a conductive material on a current collector; Irradiating an ion beam over the entire primer layer to form a concave pattern to form a patterned primer layer; And forming an electrode layer including an electrode active material on the patterned primer layer.
  • the method of manufacturing an electrode for a lithium secondary battery according to an embodiment of the present invention includes forming a primer layer including a conductive material on a current collector.
  • the current collector serves to collect electrons generated by the electrochemical reaction of the electrode active material or to supply electrons required for the electrochemical reaction, and is not particularly limited as long as it has excellent conductivity and does not cause chemical change in the lithium secondary battery.
  • the current collector may form fine concavities and convexities on its surface to enhance the bonding force with the electrode active material, and may be a film, sheet, foil, or net. Various forms such as porous bodies, foams, and nonwovens can be used.
  • the thickness of the current collector is not particularly limited and may be appropriately determined depending on the use.
  • the thickness of the current collector may be 1 to 500 ⁇ m, preferably 5 to 300 ⁇ m, more preferably 10 to 150 ⁇ m.
  • the thickness of the current collector is less than the range, the durability is lowered.
  • the thickness of the current collector is exceeded, the capacity per volume of the lithium secondary battery may be reduced.
  • the primer layer serves to increase the adhesion of the electrode layer to the current collector while suppressing the increase of the internal resistance of the electrode as much as possible, and includes a conductive material.
  • the conductive material is not particularly limited as long as it is a component that electrically connects the current collector with the electrode active material to maintain conductivity.
  • the conductive material may be natural graphite, artificial graphite, graphene, carbon black, denka black, acetylene black, ketjen black, super-P, channel black, furnace black, lamp black, summer black, carbon nanotubes, graphite It may comprise one or more selected from the group consisting of nanofibers, carbon nanofibers, aluminum, nickel, zinc oxide, potassium titanate, titanium oxide and polyphenylene derivatives.
  • the primer layer may include a binder to fix the conductive material on the current collector, form a coating film (coating film), and promote bonding between the current collector and the electrode layer.
  • a binder to fix the conductive material on the current collector, form a coating film (coating film), and promote bonding between the current collector and the electrode layer.
  • polyvinylidene fluoride polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose (HPC), regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene
  • It may include one or more selected from the group consisting of polypropylene, ethylene-propylene-diene monomer (Ethlylene Propylene Diene Monomer; EPDM), sulfonated EPDM, styrene butadiene, fluororubber.
  • the weight ratio of the conductive material and the binder is 1:10 to 10: 1.
  • the content is less than the above range, the content of the conductive material is too small to decrease the operating characteristics of the battery due to an increase in the internal resistance. On the contrary, if the content exceeds the above range, the content of the binder is too small to obtain sufficient binding force.
  • the method of forming the primer layer may use a coating film forming method commonly used in the art.
  • Wet coating methods such as, for example, gravure coating, slot die coating, spin coating, spray coating, bar coating, dip coating; Methods such as thermal evaporation, E-beam evaporation, chemical vapor deposition (CVD), and dry coating methods such as sputtering can be used.
  • the primer layer may have a thickness of 0.1 to 10 ⁇ m, preferably 0.1 to 5 ⁇ m.
  • the thickness of the primer layer is less than the above range, it is difficult to sufficiently secure the binding force between the current collector and the electrode layer, and it is difficult to form a uniform layer.
  • the primer layer exceeds the range, the primer layer acts as a resistance to improve the electrical performance of the electrode. Can be lowered or the volume of the electrode increased.
  • the present invention it is possible to increase the binding force between the current collector and the electrode layer by forming a concave pattern over the entire primer layer through the ion beam to increase the contact area with the electrode layer to be described later.
  • a concave pattern can easily implement a nanometer-level pattern, by maximizing the adhesion area by a fine pattern it can enhance the adhesion between the current collector and the electrode layer. Accordingly, it is firmly adhered to the current collector even when the volume change of the electrode active material is charged and discharged, thereby effectively maintaining the structural stability and electrical conductivity of the electrode and preventing the performance and life of the lithium secondary battery including the same.
  • the ion beam is argon (Ar), oxygen (O 2 ), nitrogen (N 2 ), acetic acid (CH 3 COOH), methane (CH 4 ), carbon tetrafluoride (CF 4 ), silane (SiH 4 ), ammonia (NH 3 ) And trimethylaluminum ((CH 3 ) 3 Al).
  • it may be an ion beam containing Ar.
  • the ion beam may be irradiated for 1 second to 60 minutes, preferably 10 seconds to 30 minutes.
  • the ion beam may be irradiated with energy in the range of 1 to 500 keV, preferably 1 to 250 keV. If the irradiation time and energy of the ion beam is less than the above range, a concave pattern may be formed non-uniformly. On the contrary, if the irradiation time and energy of the ion beam exceed the above range, the current collector under the primer layer is exposed due to excessive irradiation to expose the adhesive force between the collector and the electrode layer. Can be reduced.
  • the shape of the concave pattern may be applied without particular limitation as long as it is generally used in the art.
  • the shape of the concave pattern may be a continuous pattern or a discontinuous pattern.
  • Cross section of the concave pattern may be at least one selected from the group consisting of square, inverted trapezoidal, curved, circular, elliptical and polygonal.
  • the concave pattern may have rounded edges, slanted edges, multi-step edges or irregular edges in order to achieve uniformity of current density without leaving a pattern forming residue.
  • a concave pattern is formed on the entire surface of the primer layer formed on the current collector 10 by irradiating an ion beam under the above conditions, thereby forming a patterned primer layer 20.
  • the ratio of the thickness T of the patterned primer layer 20 and the maximum depth D of the concave pattern may be 1: 0.01 to 1: 0.90, preferably 1: 0.10 to 0.75.
  • the width W of the concave pattern may be 1 to 1000 nm, preferably 10 to 900 nm.
  • the pitch P (pitch) of the concave pattern may be 0.5 to 800 nm, preferably 5 to 500 nm.
  • the width W of the concave pattern means the longest width of the concave pattern measured in the horizontal direction
  • the pitch (P) means the spacing of the concave pattern peak
  • the maximum depth (D) of the concave pattern The vertical distance from the highest point to the lowest point.
  • the ratio of the thickness T of the patterned primer layer 20 to the maximum depth D of the concave pattern and the width W of the concave pattern and the pitch P of the concave pattern fall within the above ranges.
  • the pattern is formed uniformly and the desired contact area increase effect can be obtained.
  • the electrode active material is not particularly limited to be used in a lithium secondary battery, and the following materials may be used in various ways.
  • the electrode active material is a negative electrode active material, for example, crystalline artificial graphite, crystalline natural graphite, amorphous hard carbon, low crystalline soft carbon, carbon black, acetylene black, Ketjen black, super-P, graphene (graphene), fibrous carbon
  • Si-based material Li x Fe 2 O 3 (0 ⁇ x ⁇ 1), Li x WO 2 (0 ⁇ x ⁇ 1), Sn x Me 1- x Me ′ y O z selected from the group consisting of: (Me: Mn, Fe, Pb, Ge; Me ': Al, B, P, Si, Group 1, Group 2, Group 3 elements of the periodic table, halogen; 0 ⁇ x ⁇ 1;1 ⁇ y ⁇ 3; 1 ⁇ metal composite oxides such as z ⁇ 8); Lithium metal; Lithium alloys; Silicon-based alloys; Tin-based alloys; SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 ,
  • the electrode layer may further include a binder, a conductive material, a filler, and the like, in addition to the electrode active material described above.
  • Types of the binder and the conductive material are as mentioned above.
  • the filler is not particularly limited as long as it is a fibrous material that suppresses the expansion of the electrode and does not cause chemical change in the lithium secondary battery.
  • Olefin polymers such as polyethylene and polypropylene; Fibrous materials, such as glass fiber and carbon fiber, can be used.
  • the electrode layer may be formed by coating, drying, and pressing an electrode active material on a current collector.
  • the present invention provides an electrode for a lithium secondary battery manufactured by the above-described manufacturing method.
  • the electrode may be an anode or a cathode.
  • the manufacturing method according to the present invention increases the contact area by forming a nanometer-sized concave pattern by irradiating an ion beam on the front surface of the primer layer introduced between the current collector and the electrode layer.
  • the patterned primer layer improves the binding strength of the electrode layer to the current collector to improve the structural stability and electrical conductivity of the electrode, and can easily form a fine pattern through the ion beam irradiation process is advantageous in terms of process efficiency and productivity.
  • the lithium secondary battery electrode according to the present invention is more suitable for a battery that easily peels between an electrode layer including a current collector and an electrode active material or between electrode active materials using an electrode active material having a large volume change as a high loading electrode.
  • the electrode is a negative electrode, and the electrode active material may be Si-based material or lithium metal.
  • the Si-based material may be at least one selected from the group consisting of SiO x (0.5 ⁇ x ⁇ 2), Si alloys, and amorphous Si.
  • the metal alloyed with Si is at least one metal selected from the group consisting of Mg, Al, Fe, Ni, Cu and Ga.
  • the lithium metal may be in the form of lithium foil or lithium metal powder.
  • the present invention provides a lithium secondary battery comprising an electrode for a lithium secondary battery according to the manufacturing method.
  • the lithium secondary battery has a structure in which a non-aqueous electrolyte is impregnated into an electrode assembly including an electrode for a lithium secondary battery and a separator manufactured according to the above-described manufacturing method.
  • an insulating thin film having high ion permeability and mechanical strength is used as the separator.
  • the pore diameter of the separator is generally from 0.01 to 10 ⁇ m, and the thickness is generally from 5 to 300 ⁇ m.
  • olefin polymers such as polypropylene of chemical resistance and hydrophobicity; Sheets or non-woven fabrics made of glass fibers or polyethylene are used.
  • the solid electrolyte such as a polymer is used as the electrolyte, the solid electrolyte may also serve as a separator.
  • the non-aqueous electrolyte is composed of a non-aqueous electrolyte and a lithium salt.
  • the non-aqueous electrolyte may be a non-aqueous organic solvent, an organic solid electrolyte, an inorganic solid electrolyte, or the like, but is not limited thereto.
  • non-aqueous organic solvent For example, N-methyl- 2-pyrrolidinone, a propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, (gamma) -Butyrolactone, 1,2-dimethoxy ethane, tetrahydroxy franc, 2-methyl tetrahydrofuran, dimethylsulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane, aceto Nitrile, nitromethane, methyl formate, methyl acetate, phosphate triester, trimethoxy methane, dioxolane derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivative, Aprotic organic solvents such as tetrahydrofuran derivatives, ethers, methyl pyroionate and ethyl propionate can be
  • organic solid electrolyte examples include polyethylene derivatives, polyethylene oxide side derivatives, polypropylene oxide derivatives, phosphate ester polymers, polyagitation lysine, polyester sulfides, polyvinyl alcohols, and polyvinylidene fluorides.
  • a polymerizer containing an ionic dissociation group, and the like can be used.
  • Examples of the inorganic solid electrolyte include Li 3 N, LiI, Li 5 NI 2 , Li 3 N-LiI-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3 , Li 4 SiO 4 , Nitrides, halides, sulfates and the like of Li, such as Li 4 SiO 4 -LiI-LiOH, Li 3 PO 4 -Li 2 S-SiS 2 , and the like, may be used.
  • the lithium salt may be used without limitation as long as it is conventionally used in the lithium secondary battery electrolyte.
  • LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF6, LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li, (CF 3 SO 2 ) 2 NLi, chloroborane lithium, lower aliphatic lithium carbonate, lithium phenyl borate, imide and the like can be used.
  • the lithium salt-containing non-aqueous electrolyte includes, for example, pyridine, triethyl phosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, for the purpose of improving charge and discharge characteristics, flame retardancy, and the like.
  • Hexaphosphate triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone, N, N-substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxy ethanol, aluminum trichloride And the like may be added.
  • a halogen-containing solvent such as carbon tetrachloride or ethylene trifluoride may be further included, and carbon dioxide gas may be further included to improve high temperature storage characteristics, and FEC (Fluoro-Ethylene) may be further included. Carbonate), PRS (Propene sultone) may be further included.
  • the shape of the lithium secondary battery is not particularly limited and may be in various shapes such as cylindrical, stacked, coin type.
  • the present invention provides a battery module including the lithium secondary battery as a unit cell, and provides a battery pack including the battery module.
  • the battery pack may be used as a power source for medium and large devices that require high temperature stability, long cycle characteristics, and high capacity characteristics.
  • Examples of the medium-to-large device include a power tool that is driven by an electric motor; Electric vehicles including electric vehicles (EVs), hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and the like; Electric motorcycles including electric bicycles (E-bikes) and electric scooters (E-scooters); Electric golf carts; Power storage systems and the like, but is not limited thereto.
  • Electric vehicles including electric vehicles (EVs), hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and the like
  • Electric motorcycles including electric bicycles (E-bikes) and electric scooters (E-scooters); Electric golf carts; Power storage systems and the like, but is not limited thereto.
  • a primer layer-forming composition containing 5% by weight of denka black, 25% by weight of polyvinylidene fluoride, and NMP was applied to one surface of a 10 ⁇ m thick copper foil, followed by drying to form a primer layer having a thickness of 3 ⁇ m. .
  • a 100 keV energy Ar ion beam was irradiated on the surface of the primer layer for 1 minute to form a concave pattern of a rectangular cross section (pattern maximum depth D 1 ⁇ m, pattern width W 100 ⁇ m, pattern pitch P 10 ⁇ m). It was.
  • a lithium foil having a thickness of 20 ⁇ m was laminated on the patterned primer layer to prepare a negative electrode for a lithium secondary battery.
  • the electrode layer was formed by applying a negative electrode slurry having a thickness of 95: 2: 3 mixed with graphite: carbon black: AD-B01 (manufactured by LGC) on a patterned primer layer in a 95: 2: 3 weight ratio and drying to form an electrode layer.
  • a negative electrode slurry having a thickness of 95: 2: 3 mixed with graphite: carbon black: AD-B01 (manufactured by LGC) on a patterned primer layer in a 95: 2: 3 weight ratio and drying to form an electrode layer.
  • AD-B01 manufactured by LGC
  • a 150 keV energy CF 4 ion beam was irradiated for 5 minutes to form a concave pattern of a rectangular cross section (pattern maximum depth (D) 2 ⁇ m, pattern width (W) 100 ⁇ m, pattern pitch (P) 10 ⁇ m).
  • a negative electrode for a lithium secondary battery was manufactured in the same manner as in Example 1, except that one was used.
  • LiNi 0 instead of lithium foil on the patterned primer layer . 6 Co 0 . 2 Mn 0 .2
  • NCM 622 Super-P: The same as in Example 1 except that the positive electrode slurry mixed with a polyvinylidene fluoride in a weight ratio of 95: 2.5: 2.5 was applied to a thickness of 20 ⁇ m and dried to form an electrode layer A positive electrode for a lithium secondary battery was prepared by the method.
  • a negative electrode for a lithium secondary battery was manufactured in the same manner as in Example 1, except that the primer layer was not formed.
  • a negative electrode for a lithium secondary battery was manufactured in the same manner as in Example 1, except that no pattern was formed on the surface of the primer layer.
  • a negative electrode for a lithium secondary battery was manufactured in the same manner as in Example 1, except that a pattern was formed on the surface of the primer layer through microcontact printing.
  • the contact area of the lithium secondary battery anodes prepared according to the above Examples and Comparative Examples was calculated by optical microscope observation, and the adhesion was measured using an adhesion force meter (LR-5K, manufactured by LLOYD). The results obtained at this time are shown in Table 1 below.
  • the positive electrode active material slurry consisting of 95% by weight, 2.5% by weight and 2.5% by weight of LiCoO 2 as a positive electrode active material, Super P as a conductive material, and polyvinylidene fluoride (PVDF) as a binder, the positive electrode active material slurry was coated on an aluminum current collector and then dried to prepare a positive electrode.
  • LiCoO 2 LiCoO 2
  • Super P as a conductive material
  • PVDF polyvinylidene fluoride
  • the electrodes prepared according to Examples 1 to 3 and Comparative Examples 1 to 3 were used as the negative electrode.
  • the electrode prepared according to Example 4 was used as the positive electrode.
  • a lithium foil having a thickness of 20 ⁇ m was used as the negative electrode.
  • Table 1 it can be seen that the case of the embodiment according to the manufacturing method of the present invention is superior in contact area and adhesive strength than the comparative example. That is, by forming a concave pattern on the surface of the primer layer as in the embodiment, the contact area is increased to improve the binding force of the electrode layer to the current collector, thereby improving structural stability and conductivity of the electrode.
  • the embodiment including the primer layer patterned as shown in Table 2 is superior in the initial charge and charge efficiency and capacity characteristics compared to the comparative example.
  • lithium secondary battery electrode 10 current collector
  • the manufacturing method for the lithium secondary battery of the present invention can effectively form a fine pattern on the surface of the primer layer, thereby improving the adhesion characteristics between the current collector and the electrode active material to enable high capacity, high stability and long life of the lithium secondary battery. .

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

La présente invention concerne un procédé de fabrication d'une électrode pour un accumulateur au lithium, et une électrode pour un accumulateur au lithium ainsi fabriquée. Plus spécifiquement, le procédé comprend les étapes consistant à : former une couche d'apprêt comprenant un matériau conducteur sur un collecteur de courant ; à irradier un faisceau d'ions sur la totalité de la couche d'apprêt afin de former un motif concave et ainsi une couche d'apprêt à motif ; et à former une couche d'électrode comprenant un matériau actif d'électrode sur la couche d'apprêt à motif. De par l'interposition d'une couche d'apprêt à motif entre un collecteur de courant et une couche d'électrode, la présente invention permet d'améliorer la sécurité structurelle et la conductivité dans l'électrode, ce qui conduit à l'amélioration des performances et de la durée de vie de l'accumulateur au lithium.
PCT/KR2017/009586 2016-09-01 2017-09-01 Procédé de fabrication d'électrode pour accumulateur au lithium et électrode pour accumulateur au lithium ainsi fabriquée WO2018044112A2 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP17847037.3A EP3401984B1 (fr) 2016-09-01 2017-09-01 Procédé de fabrication d'électrode pour accumulateur au lithium et électrode pour accumulateur au lithium ainsi fabriquée
US16/076,433 US10930967B2 (en) 2016-09-01 2017-09-01 Method for manufacturing electrode for lithium secondary battery, and electrode for lithium secondary battery manufactured thereby
CN201780013803.2A CN108701817B (zh) 2016-09-01 2017-09-01 制备用于锂二次电池的电极的方法以及由此制备的用于锂二次电池的电极

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20160112645 2016-09-01
KR10-2016-0112645 2016-09-01
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