WO2018174616A1 - Composition de pré-dispersion de matériau actif d'électrode positive, électrode positive pour batterie secondaire, et batterie secondaire au lithium la comprenant - Google Patents

Composition de pré-dispersion de matériau actif d'électrode positive, électrode positive pour batterie secondaire, et batterie secondaire au lithium la comprenant Download PDF

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WO2018174616A1
WO2018174616A1 PCT/KR2018/003391 KR2018003391W WO2018174616A1 WO 2018174616 A1 WO2018174616 A1 WO 2018174616A1 KR 2018003391 W KR2018003391 W KR 2018003391W WO 2018174616 A1 WO2018174616 A1 WO 2018174616A1
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positive electrode
active material
electrode active
secondary battery
hnbr
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PCT/KR2018/003391
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English (en)
Korean (ko)
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안병훈
유흥식
구창완
하현철
최상훈
이종원
김동현
권계민
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주식회사 엘지화학
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Priority to EP18772020.6A priority Critical patent/EP3525270B8/fr
Priority to CN201880003914.XA priority patent/CN109845005B/zh
Priority to US16/338,154 priority patent/US11038175B2/en
Priority to JP2019551626A priority patent/JP7041814B2/ja
Priority to PL18772020T priority patent/PL3525270T3/pl
Priority claimed from KR1020180033253A external-priority patent/KR102178878B1/ko
Publication of WO2018174616A1 publication Critical patent/WO2018174616A1/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
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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 positive electrode active material line dispersion composition, a slurry composition for a secondary battery positive electrode, a secondary battery positive electrode and a lithium secondary battery comprising the same.
  • lithium secondary batteries having high energy density and voltage, long cycle life, and low self discharge rate have been commercialized and widely used.
  • lithium-containing cobalt oxide LiCoO 2
  • the lithium-containing cobalt oxide has thermal characteristics due to destabilization of crystal structure due to de-lithium. Since it is very poor and expensive, there was a problem that it is difficult to mass-produce a lithium secondary battery.
  • lithium iron phosphate which has a high voltage stability of about 3.5 mAh, a high volume density of about 3.6 g / cm 3 , and a theoretical capacity of about 170 mAh / g, has high temperature stability compared to cobalt, and is also inexpensive. 4 ) -based compound is illuminated as a positive electrode active material of a lithium secondary battery.
  • the lithium iron phosphate-based positive electrode active material has a structurally very stable positive electrode active material, but has a low electrical conductivity and ion conductivity. Accordingly, the surface of the lithium iron phosphate-based positive electrode active material is coated with carbon to improve electrical conductivity, and the particle size of the lithium iron phosphate-based positive electrode active material is reduced to apply ionic conductivity.
  • the present invention suppresses the aggregation of the lithium iron phosphate-based positive active material having a reduced particle size, improves dispersibility, lowers the viscosity, improves the flow, and increases the content of the final solid content, the pre-dispersion composition, secondary battery positive electrode To provide a slurry composition, a secondary battery positive electrode and a lithium secondary battery comprising the same.
  • the present invention includes a lithium iron phosphate-based positive electrode active material, a dispersant and a solvent, and the dispersant provides a positive electrode active material predispersed composition including a hydrogenated nitrile butadiene rubber (HNBR).
  • HNBR hydrogenated nitrile butadiene rubber
  • the present invention provides a slurry composition for a secondary battery positive electrode, further comprising a conductive material and a binder in the positive electrode active material line dispersion composition.
  • the present invention provides a secondary battery positive electrode prepared using a slurry composition for secondary battery positive electrode and a lithium secondary battery comprising the same.
  • the present invention it is possible to suppress the aggregation of the lithium iron phosphate-based positive electrode active material having a reduced particle size, to improve dispersibility and to lower the particle size of the dispersion, and to improve flowability by lowering the viscosity of the positive electrode active material predispersant and the positive electrode slurry. Can be improved and the content of final solids can be increased.
  • FIG. 2 is a graph showing viscosity change of dispersion time of the positive electrode active material line dispersion according to Examples 1 to 5 and Comparative Example 1.
  • FIG. 2 is a graph showing viscosity change of dispersion time of the positive electrode active material line dispersion according to Examples 1 to 5 and Comparative Example 1.
  • the positive electrode active material predispersion composition of the present invention includes a lithium iron phosphate-based positive electrode active material, a dispersant and a solvent, and the dispersant includes a hydrogenated nitrile butadiene rubber (HNBR).
  • HNBR hydrogenated nitrile butadiene rubber
  • the present invention provides a positive electrode active material pre-dispersed composition in which a lithium iron phosphate-based positive electrode active material and a dispersant are added together to pre-disperse a lithium iron phosphate-based positive electrode active material in order to improve the dispersibility of the lithium iron phosphate-based positive electrode active material.
  • a positive electrode active material predispersed composition obtained by predispersing a lithium iron phosphate positive electrode active material is prepared, and then a conductive material and a binder are mixed to prepare a positive electrode slurry composition.
  • the positive electrode active material predispersion composition of the present invention must include a dispersant
  • the present invention includes a hydrogenerated nitrile butadiene rubber (HNBR) as a dispersant of the positive electrode active material predispersion.
  • HNBR hydrogenerated nitrile butadiene rubber
  • NBR nitrile butadiene rubber
  • the hydrogenerated nitrile butadiene rubber (HNBR) dispersant may have a content of 20 to 50 wt% of the repeating unit derived from acrylonitrile (AN) based on the total weight of the hydrogenerated nitrile butadiene rubber (HNBR). Preferably from 25 to 45% by weight, most preferably from 30 to 40% by weight.
  • Hydrogenated nitrile butadiene rubber (HNBR) dispersant the hydrogenated butadiene (Hydrogenated butadiene, HBD) ratio may satisfy the following formula 1.
  • HBDwt% is the weight% of the hydrogenated butadiene (HBD) repeating unit with respect to the total weight of the hydrogenerated nitrile butadiene rubber (HNBR), and (BD + HBD) wt% is the hydrogenerated nitrile butadiene rubber ( HNBR)% by weight of repeating units derived from butadiene (BD) and repeating units derived from hydrogenated butadiene (HBD) based on the total weight.
  • HBD hydrogenated butadiene
  • HNBR hydrogenerated nitrile butadiene rubber
  • the hydrogenated butadiene (HBD) ratio of Formula 1 may be 5 to 25%, most preferably 10 to 25%.
  • HBD hydrogenated butadiene
  • the hydrogenerated nitrile butadiene rubber (HNBR) dispersant may have a weight average molecular weight (MW) of 10,000 to 700,000, more preferably 25,000 to 600,000, most preferably 200,000 to 400,000.
  • the lithium iron phosphate-based positive active material included in the positive active material line dispersion composition may be primary particles having an average particle diameter (D 50 ) of less than 1 ⁇ m.
  • Lithium iron phosphate-based positive electrode active material is a structurally very stable positive electrode active material, but has the disadvantage of low electrical conductivity and ion conductivity. Accordingly, the surface of the lithium iron phosphate-based positive electrode active material is coated with carbon to improve electrical conductivity, and the particle size of the lithium iron phosphate-based positive electrode active material is reduced to apply ionic conductivity.
  • a dispersibility of a lithium iron phosphate-based positive electrode active material having a reduced particle size by providing a positive electrode active material predispersed composition in which a lithium iron phosphate-based positive electrode active material is predispersed using a hydrogenerated nitrile butadiene rubber (HNBR) dispersant Solved the problem.
  • HNBR hydrogenerated nitrile butadiene rubber
  • the lithium iron phosphate-based positive electrode active material included in the positive electrode active material predispersion composition of the present invention may be dispersed as primary particles having an average particle diameter (D 50 ) of less than 2 ⁇ m, more preferably less than 1.2 ⁇ m, and more preferably May be dispersed as primary particles of less than 1 ⁇ m, most preferably less than 0.8 ⁇ m.
  • D 50 average particle diameter
  • the lithium iron phosphate-based positive active material may be represented by the following Chemical Formula 1.
  • M is at least one selected from the group consisting of Mn, Ni, Co, Cu, Sc, Ti, Cr, V and Zn
  • A is in the group consisting of S, Se, F, Cl and I At least one selected, and may be -0.5 ⁇ a ⁇ 0.5, 0 ⁇ x ⁇ 0.5, 0 ⁇ b ⁇ 0.1.
  • the lithium iron phosphate-based positive active material may be LiFePO 4 .
  • the lithium iron phosphate-based positive active material may be coated with a carbon-based material on the particle surface in order to improve the electrical conductivity.
  • the positive electrode active material predispersed composition may include 0.8 to 1.5 parts by weight of the hydrogenerated nitrile butadiene rubber (HNBR) dispersant based on 100 parts by weight of the positive electrode active material, more preferably 0.8 to 1.3 parts by weight, most preferably It may include 1 to 1.2 parts by weight.
  • HNBR hydrogenerated nitrile butadiene rubber
  • the hydrogenerated nitrile butadiene rubber (HNBR) dispersant is included in an amount less than 0.8 parts by weight, the surface area of the positive electrode active material increases as the particle size of the dispersion decreases, and the surface of the increased positive electrode active material does not sufficiently cover the dispersant so that the viscosity may increase significantly. If the content exceeds 1.5 parts by weight, an excess dispersant that is not adsorbed on the surface of the positive electrode active material may exist in the solvent, causing a viscosity increase.
  • the solvent may be a solvent generally used in the art, and may include dimethyl sulfoxide (DMSO), isopropyl alcohol, N-methylpyrrolidone (NMP), acetone or acetone. Water, and the like, one of these alone or a mixture of two or more thereof may be used, and more preferably, N-methylpyrrolidone (NMP) may be used.
  • DMSO dimethyl sulfoxide
  • NMP N-methylpyrrolidone
  • the viscosity of the positive active material line dispersion may be 2,000 to 20,000cps (25 °C), more preferably 9,000 to 14,000cps (25 °C), most preferably 10,000 to 13.500cps (25 °C).
  • the present invention provides a slurry composition for a secondary battery positive electrode prepared by further mixing a conductive material and a binder in the positive electrode active material line dispersion composition.
  • the slurry composition for the secondary battery positive electrode may be prepared by further mixing an additional solvent together with the mixing of the conductive material and the binder.
  • the conductive material is used to impart conductivity to the electrode.
  • the conductive material may be used without particular limitation as long as it has electrical conductivity without causing chemical change. Specific examples thereof include graphite such as natural graphite and artificial graphite; Carbon-based materials such as carbon black, acetylene black, ketzen black, channel black, furnace black, lamp black, summer black, carbon nanotubes and carbon fibers; Metal powder or metal fibers such as copper, nickel, aluminum, and silver; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; And conductive polymers such as polyphenylene derivatives.
  • the conductive material may be included in an amount of 1 to 30 wt% based on the total weight of the slurry composition for the positive electrode.
  • the binder serves to improve adhesion between the positive electrode active material particles and the adhesion between the positive electrode active material and the current collector.
  • Specific examples include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethyl cellulose (CMC).
  • the binder may be included in an amount of 1 to 30 wt% based on the total weight of the slurry composition for the positive electrode.
  • the additional solvent may be dimethyl sulfoxide (DMSO), isopropyl alcohol, N-methylpyrrolidone (NMP), acetone (acetone) or water like the positive electrode active material predispersed composition.
  • DMSO dimethyl sulfoxide
  • NMP N-methylpyrrolidone
  • acetone acetone
  • water water like the positive electrode active material predispersed composition.
  • NMP N-methylpyrrolidone
  • NMP N-methylpyrrolidone
  • the slurry composition for the positive electrode formed by using the positive electrode active material predispersed composition of the present invention has improved dispersibility of the lithium iron phosphate-based positive electrode active material, lowers the viscosity of the positive electrode slurry, improves flowability, and improves processability. Solids of the slurry can be increased.
  • the present invention provides a secondary battery positive electrode produced using the slurry composition for secondary battery positive electrode described above.
  • the secondary battery positive electrode includes a lithium iron phosphate-based positive electrode active material, a dispersant, a conductive material, and a binder, and the dispersant includes a hydrogenated nitrile butadiene rubber (HNBR).
  • HNBR hydrogenated nitrile butadiene rubber
  • the lithium iron phosphate positive electrode active material, the dispersant, the conductive material, and the binder may be the same as described above in the positive electrode active material pre-dispersion composition and the slurry composition for the positive electrode, and thus duplicated content is omitted.
  • the secondary battery positive electrode of the present invention may have improved adhesion because the binder may be evenly distributed in the positive electrode active material as the dispersibility of the lithium iron phosphate-based positive electrode active material is improved.
  • the migration phenomenon of the binder generated when volatilizing the solvent of the slurry may be reduced, thereby improving adhesion between the current collector and the positive electrode active material layer.
  • the positive electrode includes a positive electrode current collector, and a positive electrode active material layer formed on at least one surface of the positive electrode current collector, and formed using the slurry composition for the positive electrode.
  • the positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • carbon, nickel, titanium on the surface of stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel Surface treated with silver, silver or the like can be used.
  • the positive electrode current collector may have a thickness of about 3 to 500 ⁇ m, and may form fine irregularities on the surface of the current collector to increase the adhesion of the positive electrode active material.
  • it can be used in various forms, such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven body.
  • the positive electrode may be manufactured according to a conventional positive electrode manufacturing method except for using the slurry composition for the positive electrode.
  • the composition for the positive electrode slurry may be prepared by applying it on a positive electrode current collector, followed by drying and rolling.
  • the positive electrode may be prepared by casting the slurry composition for the positive electrode on a separate support, and then laminating the film obtained by peeling from the support onto a positive electrode current collector.
  • an electrochemical device including the anode is provided.
  • the electrochemical device may be specifically a battery, a capacitor, or the like, and more specifically, a lithium secondary battery.
  • the lithium secondary battery specifically includes a positive electrode, a negative electrode positioned to face the positive electrode, a separator and an electrolyte interposed between the positive electrode and the negative electrode, and the positive electrode is as described above.
  • the lithium secondary battery may further include a battery container for accommodating the electrode assembly of the positive electrode, the negative electrode, and the separator, and a sealing member for sealing the battery container.
  • the negative electrode includes a negative electrode current collector and a negative electrode active material layer positioned on the negative electrode current collector.
  • the negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
  • the negative electrode current collector may be formed on a surface of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper, or stainless steel. Surface-treated with carbon, nickel, titanium, silver, and the like, aluminum-cadmium alloy and the like can be used.
  • the negative electrode current collector may have a thickness of 3 ⁇ m to 500 ⁇ m, and similarly to the positive electrode current collector, fine concavities and convexities may be formed on the surface of the current collector to enhance the bonding force of the negative electrode active material.
  • it can be used in various forms, such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven body.
  • the negative electrode active material layer optionally includes a binder and a conductive material together with the negative electrode active material.
  • a compound capable of reversible intercalation and deintercalation of lithium may be used.
  • Specific examples include carbonaceous materials such as artificial graphite, natural graphite, graphitized carbon fibers, and amorphous carbon;
  • Metallic compounds capable of alloying with lithium such as Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si alloys, Sn alloys or Al alloys;
  • a composite including the metallic compound and the carbonaceous material such as a Si-C composite or a Sn-C composite, and any one or a mixture of two or more thereof may be used.
  • a metal lithium thin film may be used as the anode active material.
  • the carbon material both low crystalline carbon and high crystalline carbon can be used. Soft crystalline carbon and hard carbon are typical low crystalline carbon, and high crystalline carbon is amorphous, plate, scaly, spherical or fibrous natural graphite or artificial graphite, Kish graphite (Kish) graphite, pyrolytic carbon, mesophase pitch based carbon fiber, meso-carbon microbeads, mesophase pitches and petroleum or coal tar pitch High-temperature calcined carbon such as derived cokes is typical.
  • the binder and the conductive material may be the same as described above in the positive electrode.
  • the negative electrode active material layer is, for example, coated with a negative electrode active material, and optionally a composition for forming a negative electrode active material layer prepared by dissolving or dispersing a binder and a conductive material in a solvent and dried, or for forming the negative electrode active material layer
  • the composition may be prepared by casting the composition on a separate support, and then laminating the film obtained by peeling from the support onto a negative electrode current collector.
  • the separator is to separate the negative electrode and the positive electrode and to provide a passage for the movement of lithium ions, if it is usually used as a separator in a lithium secondary battery can be used without particular limitation, in particular for ion transfer of the electrolyte It is desirable to have a low resistance against the electrolyte and excellent electrolytic solution-moisture capability.
  • a porous polymer film for example, a porous polymer film made of a polyolefin-based polymer such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate copolymer or the like Laminate structures of two or more layers may be used.
  • a porous nonwoven fabrics such as nonwoven fabrics made of high melting point glass fibers, polyethylene terephthalate fibers and the like may be used.
  • a coated separator containing a ceramic component or a polymer material may be used to secure heat resistance or mechanical strength, and may be optionally used as a single layer or a multilayer structure.
  • examples of the electrolyte used in the present invention include an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel polymer electrolyte, a solid inorganic electrolyte, a molten inorganic electrolyte, and the like, which can be used in manufacturing a lithium secondary battery. It doesn't happen.
  • the electrolyte may include an organic solvent and a lithium salt.
  • the organic solvent may be used without particular limitation as long as it can serve as a medium through which ions involved in the electrochemical reaction of the battery can move.
  • the organic solvent may be an ester solvent such as methyl acetate, ethyl acetate, ⁇ -butyrolactone or ⁇ -caprolactone; Ether solvents such as dibutyl ether or tetrahydrofuran; Ketone solvents such as cyclohexanone; Aromatic hydrocarbon solvents such as benzene and fluorobenzene; Dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (MEC), ethyl methyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate, Carbonate solvents such as PC); Alcohol solvents such as ethyl alcohol and isopropyl alcohol; Nitriles, such as R-CN (R is a C2-C20 linear, branched or cyclic hydrocarbon group, which may include
  • carbonate-based solvents are preferable, and cyclic carbonates having high ionic conductivity and high dielectric constant (for example, ethylene carbonate or propylene carbonate) that can improve the charge and discharge performance of a battery, and low viscosity linear carbonate compounds (for example, a mixture of ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate and the like is more preferable.
  • the cyclic carbonate and the chain carbonate may be mixed and used in a volume ratio of about 1: 1 to about 1: 9, so that the performance of the electrolyte may be excellent.
  • the lithium salt may be used without particular limitation as long as it is a compound capable of providing lithium ions used in a lithium secondary battery.
  • the lithium salt is LiPF 6 , LiClO 4 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAl0 4 , LiAlCl 4 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiN (C 2 F 5 SO 3 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) 2 .
  • LiCl, LiI, or LiB (C 2 O 4 ) 2 and the like can be used.
  • the concentration of the lithium salt is preferably used within the range of 0.1 to 2.0M. When the concentration of the lithium salt is included in the above range, since the electrolyte has an appropriate conductivity and viscosity, it can exhibit excellent electrolyte performance, and lithium ions can move effectively.
  • the electrolyte includes, for example, haloalkylene carbonate-based compounds such as difluoro ethylene carbonate, pyridine, tri Ethyl phosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone, N, N-substituted imida
  • One or more additives such as zolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxy ethanol or aluminum trichloride may be included. In this case, the additive may be included in 0.1 to 5% by weight based on the total weight of the electrolyte.
  • the lithium secondary battery including the cathode active material according to the present invention stably exhibits excellent discharge capacity, output characteristics, and capacity retention rate
  • portable devices such as mobile phones, notebook computers, digital cameras, and hybrid electric vehicles ( It is useful for electric vehicle fields such as hybrid electric vehicle (HEV).
  • HEV hybrid electric vehicle
  • a battery module including the lithium secondary battery as a unit cell and a battery pack including the same are provided.
  • the battery module or the battery pack is a power tool (Power Tool); Electric vehicles including electric vehicles (EVs), hybrid electric vehicles, and plug-in hybrid electric vehicles (PHEVs); Or it can be used as a power source for any one or more of the system for power storage.
  • Power Tool Electric vehicles including electric vehicles (EVs), hybrid electric vehicles, and plug-in hybrid electric vehicles (PHEVs); Or it can be used as a power source for any one or more of the system for power storage.
  • the external shape of the lithium secondary battery of the present invention is not particularly limited, but may be cylindrical, square, pouch type, or coin type using a can.
  • the lithium secondary battery according to the present invention may not only be used in a battery cell used as a power source for a small device, but also preferably used as a unit battery in a medium-large battery module including a plurality of battery cells.
  • LiFePO 4 positive electrode active material having an average particle diameter (D 50 ) of 1 ⁇ m
  • 1 part by weight of an HNBR dispersant 37% by weight of AN, 21% by weight of HBD
  • 65.7 parts by weight of an NMP solvent were mixed, and a homo mixer was used. The wet process was performed for 30 minutes. After the bead mill (Beads mill (Beads size 1mm) using a circulation process for 90 minutes at 3,000rpm to prepare a positive electrode active material pre-dispersion composition.
  • Beads mill Beads size 1mm
  • a positive electrode active material predispersion composition was prepared in the same manner as in Example 1 except that 0.5 parts by weight of HNBR dispersant was mixed.
  • a positive electrode active material predispersion composition was prepared in the same manner as in Example 1 except that 2 parts by weight of an HNBR dispersant was mixed.
  • a positive electrode active material pre-dispersion composition was prepared in the same manner as in Example 1 except that 1 part by weight of an HNBR dispersant (AN 37 wt%, HBD ratio 12%) was mixed.
  • a positive electrode active material pre-dispersion composition was prepared in the same manner as in Example 1 except that 1 part by weight of an HNBR dispersant (AN 37 wt%, HBD ratio 25%) was mixed.
  • a LiFePO 4 positive electrode active material having an average particle diameter (D 50 ) of 1 ⁇ m, and 66.7 parts by weight of an NMP solvent were mixed, and a wet process was performed for 30 minutes using a Homo mixer. Thereafter, a circulation process was performed for 15 minutes at 3,000 rpm using a beads mill (Beads size 1 mm) to prepare a cathode active material predispersed composition.
  • Comparative Example 2 in which a positive electrode slurry was prepared by adding a positive electrode active material, a conductive material, and a binder at a time without preparing the positive electrode active material predispersant, dispersion of the positive electrode active material was not sufficiently performed, resulting in about 30 ⁇ m of macromolecules. . When such a large amount is generated, surface defects such as clogging of the filter or granules on the coating surface may occur in the positive electrode slurry coating process.
  • Particle size was measured using Malvern's Mastersizer 3000, and the measurement method was measured by diluting 1000 times in 3 ml of the positive electrode active material pre-dispersion every 15 minutes, the particle size was shown in Table 1 and FIG.
  • Viscosity was measured using a Brookfield DV2T viscometer, and the measuring method was measured by measuring 250 ml of the positive electrode active material predispersion every 15 minutes in a beaker, and the results are shown in Table 2 and FIG. 2.
  • Dispersant Content (parts by weight) Particle size by dispersion time (D 50 ) ( ⁇ m) 15min 30min 45min 60min 75 min 90min
  • Example 1 One 1.03 0.95 0.87 0.84 0.80 0.77
  • Example 2 0.5 1.07 0.99 0.93 0.86 0.82 0.79
  • Example 3 2 1.03 0.94 0.87 0.82 0.77 0.74
  • Example 4 One 1.05 0.98 0.90 0.88 0.85 0.81
  • Example 5 One 1.03 0.94 0.86 0.82 0.78 0.74 Comparative Example 1 - 1.28 - - - - - - -
  • Dispersant Content (parts by weight) Viscosity by Dispersion Time (cps, 25 °C, 12rpm, # 6-pin) 15min 30min 45min 60min 75 min 90min
  • Example 1 One 1,917 3,333 4,417 6,667 9,083 13,500
  • Example 2 0.5 2,583 4,750 8,830 14,580 22,670 29,920
  • Example 3 2 5,500 9,417 11,580 13,750 16,330 19,580
  • Example 4 One 2,840 4,120 5,240 7,790 13,520 18,520
  • Example 5 One 1,880 3,150 4,140 5,520 8,010 11,670 Comparative Example 1 - 28,000 - - - - - - -
  • the positive electrode active material predispersed having a low viscosity could be manufactured by using an appropriate amount of the dispersant while the dispersion particle size was reduced.

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Abstract

La présente invention concerne une composition de pré-dispersion de matériau actif d'électrode positive comprenant : un matériau actif d'électrode positive à base de phosphate de fer de lithium ; un dispersant ; et un solvant, le dispersant comprenant du caoutchouc nitrile butadiène hydrogéné (HNBR), une composition pâteuse pour une électrode positive de batterie secondaire et une électrode positive pour une batterie secondaire qui sont produites à l'aide de celle-ci, et une batterie secondaire au lithium la comprenant.
PCT/KR2018/003391 2017-03-22 2018-03-22 Composition de pré-dispersion de matériau actif d'électrode positive, électrode positive pour batterie secondaire, et batterie secondaire au lithium la comprenant WO2018174616A1 (fr)

Priority Applications (5)

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EP18772020.6A EP3525270B8 (fr) 2017-03-22 2018-03-22 Composition de pré-dispersion de matériau actif d'électrode positive, électrode positive pour batterie secondaire, et batterie secondaire au lithium comprenant l' électrode positive
CN201880003914.XA CN109845005B (zh) 2017-03-22 2018-03-22 正极活性材料预分散体组合物、二次电池用正极以及包含该正极的锂二次电池
US16/338,154 US11038175B2 (en) 2017-03-22 2018-03-22 Positive electrode active material pre-dispersion composition including hydrogenated nitrile butadiene rubber as dispersant, positive electrode for secondary battery, and lithium secondary battery including the positive electrode
JP2019551626A JP7041814B2 (ja) 2017-03-22 2018-03-22 正極活物質プレ分散体組成物、二次電池用正極、およびそれを含むリチウム二次電池
PL18772020T PL3525270T3 (pl) 2017-03-22 2018-03-22 Kompozycja wstępnej dyspersji materiału czynnego elektrody dodatniej, elektroda dodatnia dla akumulatora oraz akumulator litowy zawierający elektrodę dodatnią

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KR10-2017-0036334 2017-03-22
KR20170036334 2017-03-22
KR1020180033253A KR102178878B1 (ko) 2017-03-22 2018-03-22 양극 활물질 선분산체 조성물, 이차전지용 양극 및 이를 포함하는 리튬 이차전지
KR10-2018-0033253 2018-03-22

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WO2020206606A1 (fr) * 2019-04-09 2020-10-15 Arlanxeo Deutschland Gmbh Composition de liant pour cathode de batterie au lithium-ion, composition pâteuse de cathode, cathode et batterie l'incorporant
WO2020235760A1 (fr) * 2019-05-17 2020-11-26 한국기계연구원 Additif pour batterie secondaire, suspension d'électrode le comprenant pour batterie secondaire, et batterie secondaire
JP2022079612A (ja) * 2019-10-09 2022-05-26 三菱マテリアル株式会社 負極材料、電池、負極材料の製造方法、及び電池の製造方法
CN114174384A (zh) * 2020-01-07 2022-03-11 株式会社Lg化学 预分散剂组合物、和包括所述预分散剂组合物的电极和二次电池
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