WO2021085894A1 - Matériau liant d'anode pour batterie secondaire au lithium, et liant d'anode comprenant un produit durci associé - Google Patents

Matériau liant d'anode pour batterie secondaire au lithium, et liant d'anode comprenant un produit durci associé Download PDF

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Publication number
WO2021085894A1
WO2021085894A1 PCT/KR2020/013964 KR2020013964W WO2021085894A1 WO 2021085894 A1 WO2021085894 A1 WO 2021085894A1 KR 2020013964 W KR2020013964 W KR 2020013964W WO 2021085894 A1 WO2021085894 A1 WO 2021085894A1
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Prior art keywords
negative electrode
lithium secondary
styrene
butadiene
binder composition
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PCT/KR2020/013964
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English (en)
Korean (ko)
Inventor
이성진
손정만
류동조
한선희
한정섭
강민아
우정은
최철훈
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주식회사 엘지화학
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Priority claimed from KR1020200131978A external-priority patent/KR20210052240A/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN202080006435.0A priority Critical patent/CN113474923B/zh
Priority to US17/299,613 priority patent/US20220020992A1/en
Priority to PL20880581.2T priority patent/PL3883023T3/pl
Priority to EP20880581.2A priority patent/EP3883023B1/fr
Publication of WO2021085894A1 publication Critical patent/WO2021085894A1/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
    • 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
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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 negative electrode binder material for a lithium secondary battery, and a negative electrode binder including a cured product thereof.
  • the negative electrode of the lithium secondary battery may include a negative electrode active material that stores lithium ions during charging and releases them during discharge; A conductive material for securing an electrically conductive path while filling a space that cannot be filled by the negative active material; It is composed of a binder that physically couples these to the current collector.
  • the negative electrode binder plays an important role in physically stabilizing the negative electrode by buffering the volume change of the negative electrode active material during repetitive charging and discharging of the battery, in addition to the role of physically bonding the negative electrode active material and the conductive material.
  • negative electrode binders e.g., styrene-butadiene-based polymers, styrene-acrylate-based polymers, etc.
  • styrene-butadiene-based polymers e.g., styrene-butadiene-based polymers, styrene-acrylate-based polymers, etc.
  • problems such as deterioration of the negative electrode due to weakening of the bonding force during repeated charging and discharging of the battery and not being able to buffer the volume change of the negative electrode active material.
  • the present invention as a prerequisite for improving the performance of a lithium secondary battery, it is intended to provide a raw material that can be converted into a negative electrode binder having heat resistance, chemical resistance, excellent bonding strength and durability.
  • a vulcanization accelerator including a metal-organic framework (MOF); Styrene-butadiene-based copolymer; And it provides a negative electrode binder material for a lithium secondary battery comprising a sulfur molecule (S 8 ).
  • MOF metal-organic framework
  • S 8 sulfur molecule
  • the negative electrode binder raw material of the above embodiment may be cured while being applied to the negative electrode current collector to exhibit excellent properties such as heat resistance, chemical resistance, and mechanical properties.
  • the negative electrode binder converted from the raw material of the above embodiment is not denatured or destroyed even when high temperature is applied when manufacturing the negative electrode and the electrode assembly including the same, and side reactions with the electrolyte in the battery are suppressed, and the battery is repeatedly charged and discharged. It can contribute to improving the performance of a lithium secondary battery by maintaining excellent bonding strength and effectively buffering the volume change of the negative active material.
  • copolymerization may mean block copolymerization, random copolymerization, graft copolymerization or alternating copolymerization
  • copolymer refers to block copolymer, random copolymer, graft copolymer or alternating copolymer It can mean consolidation.
  • a material for a negative electrode binder for a lithium secondary battery comprising a vulcanization accelerator including a metal-organic framework (MOF) is provided.
  • MOF metal-organic framework
  • the styrene-butadiene-based copolymer is a polymer having a chain structure including a styrene repeating unit and a butadiene repeating unit, and a sulfur molecule (S 8 ) is a vulcanization reaction with the styrene-butadiene-based copolymer. This is a possible vulcanizing agent.
  • Vulcanization refers to a reaction forming a cured product having a network structure by forming a crosslinked bond including an S-S bond within a polymer chain and between different polymer chains.
  • the styrene-butadiene-based copolymer and the raw material composed of only sulfur molecules can undergo a vulcanization reaction only when a high temperature of about 159° C. or higher is applied.
  • sulfur molecule (S 8 ) is an octagonal ring-shaped molecule, and can be polymerized (ie, vulcanized) in the styrene-butadiene-based copolymer only by ring-opening at a temperature of about 159° C. or higher to form a radical.
  • the melting point of the styrene-butadiene-based copolymer is about 160 to 200 °C, and is denatured or destroyed at a higher temperature, so that the vulcanization reaction proceeds slowly, and the physical properties of the vulcanization reaction product may be deteriorated.
  • sulfur is activated using a vulcanization accelerator such as N,N-dicyclohexyl-2-benzothiazolesulfenamide (N,N-Dicyclohexyl-2-benzothiazolesulfenamide, DCBS) or ZnO. It is known to change the state and promote vulcanization.
  • a vulcanization accelerator such as N,N-dicyclohexyl-2-benzothiazolesulfenamide (N,N-Dicyclohexyl-2-benzothiazolesulfenamide, DCBS) or ZnO.
  • a negative electrode binder material including a metal-organic framework (MOF) in addition to the styrene-butadiene-based copolymer and sulfur molecules, a negative electrode binder material including a metal-organic framework (MOF) has been provided.
  • MOF metal-organic framework
  • the metal-organic skeleton may include metal ions or clusters; And it is a two-dimensional or three-dimensional structure comprising an organic ligand coordinated thereto.
  • the metal-organic skeleton has its own pores due to the coordination of metals and organics, and the size and shape of the pores vary according to the type of the metal-organic skeleton. Due to the presence or absence of the pores in the vulcanization reaction, unreacted monomers enter and exit the pores during the vulcanization crosslinking reaction, and the polymer-polymer crosslinking reaction is more effectively performed than the polymer-unreacted monomer reaction.
  • the metal-organic skeleton selectively promotes crosslinking between polymer chains, thereby remarking its characteristics.
  • the metal-organic skeleton has its own pores, so the mobility of lithium ions during electrode manufacturing is improved. It can contribute to the improvement of battery performance.
  • the negative electrode binder raw material of the embodiment includes the vulcanization accelerator including the metal-organic framework (MOF), so that 70 to 90 applied for drying while applied to the negative electrode current collector It is rapidly cured by hot air at °C and can exhibit excellent properties such as heat resistance, chemical resistance, and mechanical properties.
  • MOF metal-organic framework
  • the binder converted from the negative electrode binder raw material of the above embodiment is not denatured or destroyed even when high temperature is applied when manufacturing the negative electrode and the electrode assembly including the same, and side reactions with the electrolyte in the battery are suppressed, and the battery is repeatedly charged. It can contribute to improving the performance of the lithium secondary battery by maintaining excellent bonding strength even during discharge and effectively buffering the volume change of the negative electrode active material.
  • ZnDBC is used alone as a vulcanization accelerator without the help of other vulcanization accelerators such as ZnO
  • there is a limit to increasing the degree of vulcanization (crosslinking) in this regard, one method is to increase the degree of vulcanization (crosslinking) by adding another vulcanization accelerator, such as ZnO, in addition to ZnDBC, if a cathode is desired that has a higher cathode adhesion and lower expansion rate while lowering the resistance of the cathode.
  • ZnO vulcanization accelerator
  • BDC Zn (1,4-Benzenedicarboxylate)
  • the styrene-butadiene-based copolymer is a copolymer having a chain structure including a styrene repeating unit and a butadiene repeating unit, and is not particularly limited as long as it can be converted into a network structure by a vulcanization reaction.
  • the styrene-butadiene-based copolymer is generally selectable from styrene-butadiene-based copolymers known as negative electrode binders, and includes an acrylic-styrene-butadiene copolymer, a styrene-butadiene polymer, or a mixture thereof. It may be, and may further include a butadiene polymer.
  • the styrene-butadiene-based copolymer may be commercially available or may be directly prepared and used.
  • styrene-butadiene-based copolymer When the styrene-butadiene-based copolymer is directly prepared and used, a monomer mixture comprising a styrene monomer and a butadiene monomer together with a polymerization initiator generally known in the art, and optionally an acrylic monomer, etc. By emulsion polymerization in, it can be prepared into a latex-type composition containing styrene-butadiene-based copolymer particles.
  • polymerization initiator paramenthane hydroperoxide (PMHP), potassium persulfate, sodium persulfate, ammonium persulfate, and sodium bisulfate At least one polymerization initiator selected from the group containing) may be used.
  • PMHP paramenthane hydroperoxide
  • potassium persulfate potassium persulfate
  • sodium persulfate sodium persulfate
  • ammonium persulfate sodium bisulfate
  • At least one polymerization initiator selected from the group containing may be used.
  • the sulfur molecule is 0.5 to 3 parts by weight, and the metal-organic skeleton may be blended so that 0.5 to 2 parts by weight. have.
  • a crosslinking bond including a disulfide bond is formed at an appropriate level within the styrene-butadiene-based copolymer chain and between different polymer chains, while promoting and reacting vulcanization by the metal-organic skeleton. Participation can take place effectively.
  • the blending of the raw materials may be changed according to the desired physical properties.
  • the lower limit of the content of the sulfur molecule is set to 0.05 or more, 0.1 or more, 0.5 or more, or 1 or more, and the upper limit is 5 or less, 3 or less, 1 or less, or It can be made 0.5 or less.
  • the lower limit of the content of the metal-organic skeleton may be 0.05 or more, 0.1 or more, 0.5 or more, or 1 or more, and the upper limit may be 4 or less, 2 or less, 1 or less, or 0.5 or less.
  • Vulcanization accelerators other than metal-organic skeletons Vulcanization accelerators other than metal-organic skeletons
  • a general vulcanization accelerator such as N,N-dicyclohexyl-2-benzothiazolesulfenamide (N,N-Dicyclohexyl-2-benzothiazolesulfenamide, DCBS), ZnO, etc. It is also possible to add.
  • the N,N-dicyclohexyl-2-benzothiazolesulfenamide is a kind of organic vulcanization accelerator, and generally reduces the amount of vulcanizing agent (i.e., the sulfur molecule) to the polymer, while increasing the vulcanization rate to increase the vulcanization time. It is known as a material that shortens the vulcanization temperature, reduces the vulcanization temperature, and improves heat resistance, chemical resistance, bonding strength, and durability of a vulcanization reaction product.
  • the zinc oxide is a kind of inorganic vulcanization accelerator, which promotes the initial vulcanization reaction of a polymer mainly containing -COOH, and is known as a material that assists the function of the organic vulcanization accelerator.
  • the N,N-dicyclohexyl-2-benzothiazolesulfenamide and the zinc oxide may be mixed and added.
  • styrene-butadiene-based copolymer based on 100 parts by weight of the styrene-butadiene-based copolymer, 0.5 to 2 parts by weight of the N,N-dicyclohexyl-2-benzothiazolesulfenamide is added, and 0.5 to 5 parts by weight of the zinc oxide It may be added partly, wherein the weight ratio of N,N-dicyclohexyl-2-benzothiazolesulfenamide and zinc oxide may be 1:3.5 to 1:5.
  • the vulcanization reaction rate of the styrene-butadiene-based copolymer and the sulfur molecule becomes faster, the vulcanization reaction temperature is lowered, the sulfur molecule remaining after the vulcanization reaction is reduced, and the physical properties of the vulcanization reaction product can be improved. have.
  • the type of the vulcanization accelerator and the amount of the vulcanization accelerator may be determined by comprehensively considering the type of the styrene-butadiene-based copolymer and the desired negative electrode binder characteristics.
  • the negative electrode binder material of the embodiment may further include water as a solvent.
  • sodium lauryl sulfate SLS
  • sodium laureth sulfate SLES
  • ammonium lauryl sulfate Ammonium Lauryl Sulfate, ALS
  • emulsifier selected from the group.
  • the emulsifier may be blended in an amount of 0.2 to 2 parts by weight.
  • Anode binder composition for lithium secondary battery is anode binder composition for lithium secondary battery
  • a vulcanization accelerator including a metal-organic framework (MOF); containing, a negative electrode binder composition for a lithium secondary battery to provide.
  • MOF metal-organic framework
  • the styrene-butadiene-based copolymer vulcanized in the presence of a vulcanization accelerator including the metal-organic framework (MOF) is vulcanized in the presence of a vulcanization accelerator without the styrene-butadiene-based copolymer.
  • MOF metal-organic framework
  • the metal-organic skeleton has its own pores due to a coordination bond between metals and organics, and the size and shape of the pores vary according to the type of the metal-organic skeleton. Due to the presence or absence of the pores in the vulcanization reaction, unreacted monomers enter and exit the pores during the vulcanization (crosslinking) reaction, so that the polymer-polymer crosslinking reaction can be more effectively performed than the polymer-unreacted monomer reaction.
  • the metal-organic skeleton selectively promotes crosslinking between polymer chains, thereby remarking its properties.
  • the metal-organic skeleton has its own pores, so the mobility of lithium ions in the negative electrode including them is As a result, it can contribute to an increase in the CC (Constant Current) section compared to the capacity of the lithium secondary battery while lowering the internal resistance of the negative electrode.
  • CC Constant Current
  • the binder composition of the embodiment is not denatured or destroyed even when high temperature is applied in the manufacturing process of the negative electrode and the electrode assembly including the same, and side reactions with the electrolyte in the battery are suppressed, and excellent bonding strength even during repetitive charging and discharging of the battery.
  • By maintaining and effectively buffering the volume change of the negative active material it can contribute to improving the performance of the lithium secondary battery.
  • the metal-organic framework (MOF) is present in a bonded state with the vulcanized styrene-butadiene-based copolymer, or the vulcanized styrene-butadiene-based It can exist independently of the copolymer.
  • the styrene-butadiene-based copolymer in the process of vulcanizing the styrene-butadiene-based copolymer in the presence of the vulcanization accelerator including the metal-organic skeleton (MOF), the styrene-butadiene-based copolymer is vulcanized and at the same time, the metal-organic skeleton ( MOF) may be partially complexed with a styrene-butadiene-based copolymer.
  • MOF metal-organic skeleton
  • the structure of the metal-organic skeleton (MOF) is partially changed, allowing it to be complexed with the styrene-butadiene-based copolymer. have.
  • the catalyst efficiency is higher in the state of being complexed with the styrene-butadiene-based copolymer, and the vulcanization reaction can proceed more effectively.
  • the metal ions that participated in the vulcanization reaction may mostly return to the metal-organic skeleton (MOF) after the vulcanization reaction, but some may remain in an ionic state.
  • MOF metal-organic skeleton
  • the metal-organic framework (MOF) is present in a state independently mixed with the vulcanized styrene-butadiene-based copolymer, and a portion thereof is structurally changed and the vulcanized styrene- It can remain in a complexed state with a butadiene-based copolymer.
  • the negative electrode binder composition of the embodiment may have a gel content of 80% or more calculated by Equation 1 below:
  • M a is the negative electrode binder composition dried at room temperature for 24 hours and then dried at 80° C. for 24 hours to obtain a film-type binder composition, and the binder film was cut into a very pellet, and 0.5 g of the binder composition was prepared. It is the weight taken and measured,
  • M b is the negative electrode binder composition weighed by immersion in 50 g of THF (Tetrahydrofuran) for 24 hours or more, filtering through 200 Mesh, and drying the mesh and the negative electrode binder remaining in the mesh at 80° C. for 48 hours. It is the weight of the copolymer remaining in the mesh.
  • THF Tetrahydrofuran
  • the gel content refers to the degree of crosslinking of the copolymer, and is calculated as in Equation 1 and expressed as an insoluble fraction in the electrolyte.
  • the gel content in the negative electrode binder according to the embodiment may be 80% or more, 81% or more, or 82% or more. If the gel content is less than 80%, swelling of the electrolyte solution increases, and thus the life of the battery may be reduced.
  • the upper limit of the gel content is not particularly limited, but may be 99% or less, 98% or less, or 97% or less.
  • a vulcanization accelerator including a metal-organic framework (MOF)
  • MOF metal-organic framework
  • S 8 sulfur molecule
  • the vulcanization reaction may be carried out in a temperature range of 70 to 90 °C.
  • the temperature range for the vulcanization reaction is 70°C or more, or 71°C or more, or 72°C or more, or 73°C or more, or 74°C or more, or 75°C or more, while 90°C or less, or 89°C or less, or It can be adjusted within a range of 88°C or less, or 87°C or less, or 86°C or less, or 85°C or less.
  • the vulcanization reaction may be carried out for to 60 minutes.
  • the vulcanization reaction time is 1 minute or more, 3 minutes or more, 5 minutes or more, 7 minutes or more, or 9 minutes or more, and 60 minutes or less, 50 minutes or less, 40 minutes or less, 30 minutes or less, or 20 minutes or less. It can be adjusted within the range.
  • the vulcanization reaction may be performed in a state in which the negative electrode binder material is applied to the negative electrode current collector, as mentioned above.
  • the negative electrode binder material of the embodiment may include a negative electrode active material; Conductive material; Aqueous or non-aqueous solvents; It is prepared as a negative electrode slurry by mixing with etc., and is rapidly cured by hot air of 70 to 90°C applied for drying while applied on the negative electrode current collector, providing excellent properties such as heat resistance, chemical resistance, and mechanical properties. It can be an expressing negative electrode binder.
  • the vulcanization reaction may include applying heat to the negative active material slurry applied to one or both surfaces of the negative electrode current collector; And curing the anode binder material in the anode active material slurry by the heat.
  • the content of the negative electrode binder material may be 0.1 to 0.5% by weight, the content of the negative electrode active material may be 80 to 84% by weight, and the content of the binder may be 0.5 to 2.5% by weight And the balance may be an additive and a solvent.
  • the content of each substance can be adjusted according to common knowledge in the art.
  • the negative active material, the conductive material, the additive, and the like will be described later.
  • a negative electrode current collector In another embodiment of the present invention, a negative electrode current collector; And a styrene-butadiene-based copolymer, a negative electrode active material, and a conductive material vulcanized in the presence of a vulcanization accelerator located on the negative electrode current collector and including a metal-organic framework (MOF). It provides a negative electrode for a lithium secondary battery including a layer.
  • MOF metal-organic framework
  • the negative electrode of one embodiment includes a binder converted from the negative electrode binder raw material of the above-described embodiment, side reactions with the electrolyte solution in the battery are suppressed, and excellent bonding strength is maintained even during repetitive charging and discharging of the battery, and the volume of the negative electrode active material By effectively buffering the change, it can contribute to improving the performance of the lithium secondary battery.
  • the negative electrode active material layer is independently, the negative electrode active material is a material capable of reversibly intercalating/deintercalating lithium ions, lithium metal, an alloy of lithium metal, doped with lithium, and It includes a material that can be undoped, or a transition metal oxide.
  • any carbon-based negative active material generally used in lithium ion secondary batteries may be used as a carbon material, and a representative example thereof is crystalline carbon.
  • Amorphous carbon, or a combination thereof may be used.
  • the crystalline carbon include graphite such as amorphous, plate-shaped, flake, spherical or fibrous natural graphite or artificial graphite, and examples of the amorphous carbon include soft carbon (low-temperature calcined carbon).
  • hard carbon, mesophase pitch carbide, and fired coke may be used.
  • the lithium metal alloy includes lithium and a metal of Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, or Sn. Alloys can be used.
  • Materials capable of doping and undoping lithium include Si, SiO x (0 ⁇ x ⁇ 2), Si-C composites, Si-Q alloys (where Q is an alkali metal, alkaline earth metal, group 13 to group 16 element , Transition metal, rare earth element or a combination thereof, and not Si), Sn, SnO 2 , Sn-C complex, Sn-R (the R is an alkali metal, alkaline earth metal, group 13 to group 16 element, transition metal, It is a rare earth element or a combination of these, and Sn is not), etc. are mentioned.
  • Q and R include Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te, Po, or combinations thereof.
  • transition metal oxide examples include vanadium oxide and lithium vanadium oxide.
  • the negative active material layer may include at least one carbon-based negative active material selected from artificial graphite, natural graphite, soft carbon, hard carbon, or a mixture thereof.
  • the negative active material layer may further include a conductive material.
  • the conductive material is used to impart conductivity to the electrode, and in the battery constituted, any material can be used as long as it does not cause chemical change and is an electronic conductive material, such as natural graphite, artificial graphite, carbon black, acetylene black, Ketjen Carbon-based materials such as black and carbon fiber; Metal-based materials such as metal powders such as copper, nickel, aluminum, and silver, or metal fibers; Conductive polymers such as polyphenylene derivatives; Alternatively, a conductive material containing a mixture thereof may be used.
  • each of the negative electrode active material layers may independently include at least one selected from the group of carbon-based conductive materials including acetylene black, carbon black, ketjen black, carbon fiber, or a mixture thereof.
  • the conductive material is used to impart conductivity to the electrode, and any electronically conductive material can be used without causing a chemical change in the configured battery.
  • any electronically conductive material can be used without causing a chemical change in the configured battery.
  • natural graphite, artificial graphite, carbon black, acetylene black, ketjen black Carbon-based materials such as carbon fiber;
  • Metal-based materials such as metal powders such as copper, nickel, aluminum, and silver, or metal fibers;
  • Conductive polymers such as polyphenylene derivatives;
  • a conductive material containing a mixture thereof may be used.
  • a copper foil, a nickel foil, a stainless steel foil, a titanium foil, a nickel foam, a copper foam, a polymer substrate coated with a conductive metal, or a combination thereof may be used.
  • the cathode of the embodiment Electrolytes; And it provides a lithium secondary battery including a positive electrode.
  • the lithium secondary battery of the embodiment may further include a separator between the positive electrode and the negative electrode.
  • the lithium secondary battery may be classified into a cylindrical type, a square type, a coin type, a pouch type, etc. according to the shape to be used, and may be divided into a bulk type and a thin film type according to the size. Since the structure and manufacturing method of these batteries are widely known in this field, a minimum explanation will be added.
  • the positive electrode includes a current collector and a positive electrode active material layer formed on the current collector.
  • a compound capable of reversible intercalation and deintercalation of lithium (reitiated intercalation compound) may be used.
  • at least one of cobalt, manganese, nickel, or a composite oxide of lithium and a metal of a combination thereof may be used, and a specific example thereof may be a compound represented by any one of the following formulas.
  • Li a A 1-b R b D 2 (where 0.90 ⁇ a ⁇ 1.8 and 0 ⁇ b ⁇ 0.5); Li a E 1-b R b O 2-c D c (where 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, and 0 ⁇ c ⁇ 0.05); LiE 2-b R b O 4-c D c (where 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05); Li a Ni 1-bc Co b R c D ⁇ (wherein, 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05 and 0 ⁇ ⁇ 2); Li a Ni 1-bc Co b R c O 2- ⁇ Z ⁇ (wherein 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05 and 0 ⁇ ⁇ 2); Li a Ni 1-bc Co b R c O 2- ⁇ Z 2 (wherein 0.90 ⁇ a ⁇ 1.8, 0
  • A is Ni, Co, Mn, or a combination thereof;
  • R is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth elements or combinations thereof;
  • D is O, F, S, P or a combination thereof;
  • E is Co, Mn, or a combination thereof;
  • Z is F, S, P or a combination thereof;
  • G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof;
  • Q is Ti, Mo, Mn, or a combination thereof;
  • T is Cr, V, Fe, Sc, Y or a combination thereof;
  • J is V, Cr, Mn, Co, Ni, Cu, or a combination thereof.
  • the coating layer may include, as a coating element compound, oxide, hydroxide of a coating element, oxyhydroxide of a coating element, oxycarbonate of a coating element, or hydroxycarbonate of a coating element.
  • the compound constituting these coating layers may be amorphous or crystalline.
  • As a coating element included in the coating layer Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or a mixture thereof may be used.
  • the coating layer formation process is a method that does not adversely affect the physical properties of the positive electrode active material by using these elements in the compound (e.g., spray coating, dipping method, etc.), any coating method may be used.
  • any coating method may be used. The detailed description will be omitted because it can be well understood by those in the field.
  • the positive electrode active material layer also includes a binder and a conductive material.
  • the binder adheres well the positive electrode active material particles to each other, and also plays a role in attaching the positive electrode active material to the current collector well, and representative examples thereof include polyvinyl alcohol, carboxymethylcellulose, hydroxypropylcellulose, diacetylcellulose, and polyvinyl Chloride, carboxylated polyvinylchloride, polyvinylfluoride, polymer containing ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene- Butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, etc. may be used, but the present invention is not limited thereto.
  • the conductive material is used to impart conductivity to the electrode, and in the battery constituted, any material can be used as long as it does not cause chemical change and is an electronic conductive material, such as natural graphite, artificial graphite, carbon black, acetylene black, Ketjen Metal powders such as black, carbon fiber, copper, nickel, aluminum, and silver, metal fibers, etc. may be used, and conductive materials such as polyphenylene derivatives may be used alone or in combination of one or more.
  • an electronic conductive material such as natural graphite, artificial graphite, carbon black, acetylene black, Ketjen Metal powders such as black, carbon fiber, copper, nickel, aluminum, and silver, metal fibers, etc.
  • conductive materials such as polyphenylene derivatives may be used alone or in combination of one or more.
  • Al may be used as the current collector, but is not limited thereto.
  • Each of the negative electrode and the positive electrode is prepared by mixing an active material, a conductive material, and a binder in a solvent to prepare an active material composition, and then applying the composition to a current collector. Since such an electrode manufacturing method is widely known in the art, a detailed description thereof will be omitted.
  • the solvent N-methylpyrrolidone or the like may be used, but is not limited thereto.
  • the electrolyte includes a non-aqueous organic solvent and a lithium salt.
  • the non-aqueous organic solvent serves as a medium through which ions involved in the electrochemical reaction of the battery can move.
  • a carbonate-based, ester-based, ether-based, ketone-based, alcohol-based, or aprotic solvent may be used.
  • the carbonate-based solvent dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methyl ethyl carbonate (MEC), ethylene carbonate ( EC), propylene carbonate (PC), butylene carbonate (BC), and the like may be used, and as the ester solvent, methyl acetate, ethyl acetate, n-propyl acetate, 1,1-dimethylethyl acetate, methylpropionate , Ethyl propionate, ⁇ -butyrolactone, decanolide, valerolactone, mevalonolactone, caprolactone, and the like may be used.
  • Dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, etc. may be used as the ether solvent, and cyclohexanone may be used as the ketone solvent.
  • ether solvent a solvent for ether and cyclohexanone.
  • ketone solvent a solvent for ketone solvent.
  • R-CN R is a C2 to C20 linear, branched, or cyclic hydrocarbon group, wherein Amides such as nitriles such as dimethylformamide, dioxolanes such as 1,3-dioxolane, sulfolanes such as 1,3-dioxolane, and the like may be used.
  • the non-aqueous organic solvent may be used alone or in combination of one or more, and the mixing ratio in the case of using one or more mixtures may be appropriately adjusted according to the desired battery performance, which is widely understood by those in the field. Can be.
  • the electrolyte may exhibit excellent performance.
  • the non-aqueous organic solvent may further include the aromatic hydrocarbon-based organic solvent in the carbonate-based solvent.
  • the carbonate-based solvent and the aromatic hydrocarbon-based organic solvent may be mixed in a volume ratio of about 1:1 to about 30:1.
  • an aromatic hydrocarbon-based compound of Formula 1 may be used as the aromatic hydrocarbon-based organic solvent.
  • R 1 to R 6 are each independently hydrogen, halogen, a C1 to C10 alkyl group, a C1 to C10 haloalkyl group, or a combination thereof.
  • the aromatic hydrocarbon-based organic solvent is benzene, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,3-trifluorobenzene , 1,2,4-trifluorobenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2, 4-trichlorobenzene, iodobenzene, 1,2-diaiodobenzene, 1,3-diaiodobenzene, 1,4-diaiodobenzene, 1,2,3-triiodobenzene, 1,2,4 -Triiodobenzene, toluene, fluorotoluene, 1,2-difluorotoluene, 1,3-difluor
  • the non-aqueous electrolyte may further include vinylene carbonate or an ethylene carbonate-based compound of Formula 2 in order to improve battery life.
  • R 7 and R 8 are each independently hydrogen, a halogen group, a cyano group (CN), a nitro group (NO 2 ), or a C1 to C5 fluoroalkyl group, and at least one of R 7 and R 8 Is a halogen group, a cyano group (CN), a nitro group (NO 2 ), or a C1 to C5 fluoroalkyl group.
  • ethylene carbonate-based compound examples include difluoro ethylene carbonate, chloroethylene carbonate, dichloroethylene carbonate, bromoethylene carbonate, dibromoethylene carbonate, nitroethylene carbonate, cyanoethylene carbonate, fluoroethylene carbonate, and the like. I can.
  • the lifespan may be improved by appropriately adjusting the amount of the vinylene carbonate-based compound.
  • the lithium salt is dissolved in the non-aqueous organic solvent, acts as a source of lithium ions in the battery, enables the operation of a basic lithium secondary battery, and promotes the movement of lithium ions between the positive electrode and the negative electrode.
  • Representative examples of the lithium salt include LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiC 4 F 9 SO 3 , LiClO 4 , LiAlO 2 , LiAlCl 4 , LiN(C x F 2x+1 SO 2 )(C y F 2y +1 SO 2 ) (where x and y are natural numbers), LiCl, LiI, LiB(C 2 O 4 ) 2 (lithium bis(oxalato) borate; LiBOB) or a combination thereof
  • the concentration of the lithium salt is preferably within the range of 0.1 to 2.0 M. If the concentration of the lithium salt falls within the above range, the electrolyte has an appropriate conductivity and viscosity. It can exhibit
  • the separator separates the negative electrode from the positive electrode and provides a passage for lithium ions to move, and any separator commonly used in a lithium battery may be used. That is, those having low resistance to ion movement of the electrolyte and excellent in the ability to impregnate the electrolyte may be used.
  • any separator commonly used in a lithium battery may be used.
  • those having low resistance to ion movement of the electrolyte and excellent in the ability to impregnate the electrolyte may be used.
  • glass fiber polyester, Teflon, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), or a combination thereof
  • PTFE polytetrafluoroethylene
  • it may be in the form of a non-woven fabric or a woven fabric.
  • polyolefin-based polymer separators such as polyethylene, polypropylene, etc. are mainly used for lithium-ion batteries, and coated separators containing ceramic components or polymer materials may be used
  • the solid content in the composition is 30% by weight, and the number average particle diameter of the polymer particles contained therein is 50 nm (measured value by dynamic light scattering (DLS) equipment).
  • Anode binder raw material (acrylic-styrene-butadiene polymer+sulfur+Zn(BDC)+DCBS+ZnO)
  • Example 1 0.5 g of the negative electrode binder material of Example 1 was taken and added to the conductive material dispersion, 150 g of artificial graphite (D50: 20 ⁇ m), which is a negative electrode active material, and 20 g of distilled water were added thereto, followed by stirring for 10 minutes. A negative active material slurry of Example 1 was prepared.
  • a copper foil having a thickness of 20 ⁇ m was used as a negative electrode current collector, and the negative active material slurry of Example 1 was coated on one side of the negative electrode current collector using a comma coater (application amount per side: 10.8 mg /cm 2 ), hot air drying for 10 minutes in an oven at 80° C., rolling at 25° C. to a total thickness of 90 ⁇ m, and vacuum drying at 120° C. to obtain a negative electrode of Example 1.
  • a comma coater application amount per side: 10.8 mg /cm 2
  • the negative electrode was used as a working electrode, a lithium metal sheet having a thickness of 150 ⁇ m was used as a reference electrode, and a polyethylene separator (thickness: 20 ⁇ m, porosity: 40%) was inserted between the working electrode and the reference electrode.
  • a lithium secondary battery was manufactured in the form of a 2032 half-cell according to a conventional manufacturing method.
  • EC ethylene carbonate
  • PC propylene carbonate
  • DEC diethyl carbonate
  • FEC fluoroethylene carbonate
  • Anode binder raw material (acrylic-styrene-butadiene polymer+sulfur+Zn(BDC)+DCBS+ZnO)
  • Example 2 instead of the binder composition of Example 1, the negative electrode binder material of Example 2 was used, and the remainder of the negative electrode and lithium ion half battery of Example 2 were prepared in the same manner as in Example 1.
  • Anode binder raw material (acrylic-styrene-butadiene polymer+sulfur+Zn(BDC)+DCBS+ZnO)
  • Example 3 In place of the binder composition of Example 1, the negative electrode binder raw material of Example 3 was used, and the remainder of the negative electrode and lithium ion half battery of Example 3 were prepared in the same manner as in Example 1.
  • Anode binder raw material (acrylic-styrene-butadiene polymer + sulfur + Zn (BDC))
  • Example 4 instead of the binder composition of Example 1, the negative electrode binder material of Example 4 was used, and the rest were the same as those of Example 1, to prepare a negative electrode and a lithium ion half battery of Example 4.
  • anode binder raw material Acrylic-styrene-butadiene polymer alone
  • the negative electrode binder raw material of Comparative Example 1 was used, and the rest were the same as those of Example 1, to prepare a negative electrode and a lithium ion half battery of Comparative Example 1.
  • the binder composition of Comparative Example 2 was used, and the rest were the same as those of Example 1 to prepare a negative electrode and a lithium ion half battery of Comparative Example 2.
  • the binder composition of Comparative Example 3 was used, and the rest were the same as those of Example 1 to prepare a negative electrode and a lithium ion half battery of Comparative Example 3.
  • Examples 1 to 4 and Comparative Examples 1 to 3 in the process of applying heat after applying a negative electrode active material slurry including a negative electrode binder raw material, a conductive material dispersion, a negative electrode active material, and an additional solvent to a negative electrode current collector, the At the same time as the solvent in the anode active material slurry is removed to form the anode active material layer, a vulcanization reaction of the material for the anode binder occurs to convert it into a binder. In such a manufacturing process, it is impossible to separate the binder (ie, vulcanized styrene-butadiene-based copolymer) from each of the final negative electrodes of Examples 1 to 4 and Comparative Examples 1 to 3.
  • the binder ie, vulcanized styrene-butadiene-based copolymer
  • Gel content in the binder composition First, the binder composition was dried at room temperature for 24 hours, and then dried at 80° C. for 24 hours to obtain a film-type binder composition, and the binder film was cut into very small pellets, and then 0.5 Take g of the binder composition and measure the correct weight. (Ma)
  • the gel content was calculated through Equation 1 below.
  • the gel content in the negative electrode binder compositions of Examples 1 to 4 is higher.
  • the gel content refers to the degree of crosslinking of the copolymer.
  • the degree of vulcanization (crosslinking) of the vulcanized styrene-butadiene-based copolymer in the negative electrode binder compositions of Examples 1 to 4 is higher.
  • the degree of vulcanization (crosslinking) of the vulcanized styrene-butadiene-based copolymer is higher.
  • Adhesion of negative electrode When the negative electrode active material layer of each negative electrode is adhered to a glass substrate in a constant temperature chamber at 25° C., and the negative electrode is pulled at a peel rate of 5 mm/min and a peel angle of 180°, from the glass substrate. The force by which the negative active material layer of the negative electrode is peeled was measured.
  • Discharge characteristics of the battery In a constant temperature chamber at 25°C, discharge each of the lithium ion half cells 3 times in CC/CV mode from 1.5V to 5mV at 1 C, and then to 1 C in CC mode. After discharging, the discharge capacity of the CC section compared to the total discharge capacity was converted into a percentage according to Equation 2 below.
  • each battery was disassembled to recover the anode.
  • Each recovered negative electrode was washed with a DMC (dimethyl carbonate) solvent and dried within a few minutes using an air blower at room temperature, and then the thickness was measured. Accordingly, the measured thickness was substituted into the following equation to calculate the expansion rate of the negative electrode.
  • DMC dimethyl carbonate
  • Discharge negative electrode thickness of battery negative electrode thickness during one discharge of lithium ion battery
  • Thickness of copper foil thickness of negative electrode current collector in rolled electrode
  • Examples 1 to 4 showed a result of further lowering the volume resistivity of the negative active material layer, in particular, and the result improved as described above is believed to be due to Zn (DBC).
  • the metal-organic skeleton has its own pores due to a coordination bond between a metal and an organic material, and the size and shape of the pores vary according to the type of the metal-organic skeleton. Due to the presence or absence of the pores in the vulcanization reaction, unreacted monomers enter and exit the pores during the vulcanization (crosslinking) reaction, so that the polymer-polymer crosslinking reaction can be more effectively performed than the polymer-unreacted monomer reaction.
  • the metal-organic skeleton is evaluated to have outstanding properties by selectively promoting crosslinking between polymer chains.
  • the metal-organic skeleton has its own pores, so the mobility of lithium ions in the negative electrode including them is As a result, it can contribute to an increase in the CC (Constant Current) section compared to the capacity of the lithium secondary battery while lowering the internal resistance of the negative electrode.
  • CC Constant Current
  • each of the negative electrode binder raw materials of Examples 1 to 4 contained Zn (DBC) as a vulcanization accelerator, compared to Comparative Example 2 containing only DSBS as a vulcanization accelerator and Comparative Example 3 containing only ZnO. It is possible to more effectively promote the vulcanization reaction of the coalescence and sulfur molecules (S 8 ), and significantly improve the performance of the negative electrode and lithium secondary battery to which the vulcanization reaction product is applied.
  • DBC Zn
  • Examples 1 to 4 commonly exhibit the effect of lowering the resistance of the negative electrode, and in particular, Examples 1 to 3 showed higher adhesion to the negative electrode and a lower expansion rate than that of Example 4, and this result is a result of DSBS as a vulcanization accelerator. And ZnO is considered to be due to the additional inclusion.
  • ZnDBC performs its special function as well as a vulcanization accelerating role, it shows the effect of lowering the resistance of the negative electrode in Examples 1 to 4.
  • Example 4 the higher cathode adhesion and lower expansion rates in Examples 1 to 3 than in Example 4 are that when ZnDBC is used alone as a vulcanization accelerator without the aid of other vulcanization accelerators such as DSBS and ZnO, the degree of vulcanization (crosslinking) is reduced. There seems to be a limit to the height.
  • the present invention is not limited to the above embodiments, but may be manufactured in a variety of different forms, and those of ordinary skill in the art to which the present invention pertains, other specific forms without changing the technical spirit or essential features of the present invention. It will be appreciated that it can be implemented with.

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Abstract

L'objectif de la présente invention est de fournir, en tant que condition préalable pour améliorer les performances d'une batterie secondaire au lithium, un matériau qui peut être converti en un liant d'anode ayant toutes les caractéristiques suivantes à savoir une certaine résistance à la chaleur, une certaine résistance chimique, une excellente force de liaison, une certaine durabilité et similaires. Plus spécifiquement, la présente invention concerne, dans un certain mode de réalisation, un matériau liant d'anode pour une batterie secondaire au lithium qui comprend : un accélérateur de vulcanisation comprenant un réseau organométallique (MOF) ; un copolymère de styrène-butadiène ; et une molécule de soufre (S8).
PCT/KR2020/013964 2019-10-31 2020-10-14 Matériau liant d'anode pour batterie secondaire au lithium, et liant d'anode comprenant un produit durci associé WO2021085894A1 (fr)

Priority Applications (4)

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CN202080006435.0A CN113474923B (zh) 2019-10-31 2020-10-14 用于锂可充电电池的阳极粘合剂、包含该阳极粘合剂的固化产物的阳极粘合剂
US17/299,613 US20220020992A1 (en) 2019-10-31 2020-10-14 Anode Binder for Lithium Rechargeable Battery, Anode Binder Including Cured Compound of the Same Anode Binder
PL20880581.2T PL3883023T3 (pl) 2019-10-31 2020-10-14 Materiał spoiwa do anody do litowej baterii wtórnej oraz spoiwo do anody zawierające produkt jego utwardzania
EP20880581.2A EP3883023B1 (fr) 2019-10-31 2020-10-14 Matériau liant d'anode pour batterie secondaire au lithium, et liant d'anode comprenant un produit durci associé

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KR20190138185 2019-10-31
KR10-2019-0138185 2019-10-31
KR1020200131978A KR20210052240A (ko) 2019-10-31 2020-10-13 리튬 이차 전지용 음극 바인더 원료, 이의 경화물을 포함하는 음극 바인더
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012026462A1 (fr) * 2010-08-24 2012-03-01 日本ゼオン株式会社 Composition de liant pour électrode négative de batterie secondaire, composition pâteuse pour électrode négative de batterie secondaire, électrode négative de batterie secondaire, batterie secondaire, et procédé de production de composition de liant pour électrode négative de batterie secondaire
JP2017174804A (ja) * 2016-02-18 2017-09-28 福建藍海黒石科技有限公司Ｂｌｕｅ Ｏｃｅａｎ ＆ Ｂｌａｃｋ Ｓｔｏｎｅ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏ．，Ｌｔｄ．（Ｆｕｊｉａｎ） リチウムイオン電池負極用水性バインダー及びその調製方法
KR20180048554A (ko) * 2018-05-03 2018-05-10 인천대학교 산학협력단 폴리아크릴산과 폴리아닐린의 상호작용을 이용한 음극용 고분자 바인더
KR20190036700A (ko) * 2017-09-28 2019-04-05 주식회사 엘지화학 탄소-황 복합체, 그의 제조방법 및 이를 포함하는 리튬 이차전지
KR20190118278A (ko) * 2018-04-10 2019-10-18 충남대학교산학협력단 이차전지 음극용 바인더, 이를 포함하는 이차전지용 음극 및 이를 포함하는 리튬 이차 전지

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012026462A1 (fr) * 2010-08-24 2012-03-01 日本ゼオン株式会社 Composition de liant pour électrode négative de batterie secondaire, composition pâteuse pour électrode négative de batterie secondaire, électrode négative de batterie secondaire, batterie secondaire, et procédé de production de composition de liant pour électrode négative de batterie secondaire
JP2017174804A (ja) * 2016-02-18 2017-09-28 福建藍海黒石科技有限公司Ｂｌｕｅ Ｏｃｅａｎ ＆ Ｂｌａｃｋ Ｓｔｏｎｅ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏ．，Ｌｔｄ．（Ｆｕｊｉａｎ） リチウムイオン電池負極用水性バインダー及びその調製方法
KR20190036700A (ko) * 2017-09-28 2019-04-05 주식회사 엘지화학 탄소-황 복합체, 그의 제조방법 및 이를 포함하는 리튬 이차전지
KR20190118278A (ko) * 2018-04-10 2019-10-18 충남대학교산학협력단 이차전지 음극용 바인더, 이를 포함하는 이차전지용 음극 및 이를 포함하는 리튬 이차 전지
KR20180048554A (ko) * 2018-05-03 2018-05-10 인천대학교 산학협력단 폴리아크릴산과 폴리아닐린의 상호작용을 이용한 음극용 고분자 바인더

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