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WO2018182343A1 - Composition de liant pour batterie secondaire, électrode pour batterie secondaire et batterie secondaire au lithium comprenant celle-ci - Google Patents

Composition de liant pour batterie secondaire, électrode pour batterie secondaire et batterie secondaire au lithium comprenant celle-ci Download PDF

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Publication number
WO2018182343A1
WO2018182343A1 PCT/KR2018/003746 KR2018003746W WO2018182343A1 WO 2018182343 A1 WO2018182343 A1 WO 2018182343A1 KR 2018003746 W KR2018003746 W KR 2018003746W WO 2018182343 A1 WO2018182343 A1 WO 2018182343A1
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weight
acrylate
secondary battery
methacrylate
parts
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PCT/KR2018/003746
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English (en)
Korean (ko)
Inventor
윤지희
유정우
김제영
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주식회사 엘지화학
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Priority claimed from KR1020180035834A external-priority patent/KR102290957B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US16/325,500 priority Critical patent/US11024851B2/en
Priority to PL18776291T priority patent/PL3483964T3/pl
Priority to CN201880003405.7A priority patent/CN109716566B/zh
Priority to EP18776291.9A priority patent/EP3483964B1/fr
Priority to JP2019548849A priority patent/JP7034407B2/ja
Publication of WO2018182343A1 publication Critical patent/WO2018182343A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/10—Copolymers of styrene with conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—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 secondary battery binder composition, and a secondary battery electrode and a lithium secondary battery comprising the same, and more particularly to a binder composition having a suitable wet strength, a secondary battery electrode and a lithium secondary battery comprising the same.
  • An electrode of a lithium secondary battery is prepared by mixing a positive electrode active material or a negative electrode active material with a binder resin component and dispersing it in a solvent to make a slurry, and applying this to the surface of an electrode current collector to form a mixture layer after drying.
  • the binder is used to secure adhesion or binding force between the active material and the active material, and between the active material and the electrode current collector, but an excess binder is required to improve the adhesion between the electrode current collector and the active material.
  • the excess binder has a problem of lowering the electrode capacity and conductivity.
  • insufficient adhesive force causes the electrode peeling phenomenon in the process of electrode drying, pressing, etc., thereby increasing the electrode defect rate.
  • an electrode with low adhesive force may be peeled off by an external impact, and this electrode peeling may increase contact resistance between the electrode material and the current collector, which may cause deterioration of electrode output performance.
  • the binder and the use of the present invention can provide a secondary battery having improved performance by providing better adhesion and solving an electrochemical performance deterioration problem due to electrode peeling, detachment of the active material from the current collector, or a change in contact interface between the active materials.
  • the problem to be solved by the present invention is to provide a binder composition for a secondary battery that can improve the life performance of the battery by maintaining a high mechanical properties even after the electrolyte solution impregnation while providing more excellent adhesion.
  • Another object of the present invention is to provide a secondary battery electrode comprising the secondary battery binder composition.
  • Another object of the present invention is to provide a lithium secondary battery including the secondary battery electrode.
  • the present invention to solve the above problems, (a) from a unit derived from a vinyl monomer, (b) a unit derived from a conjugated diene monomer or a conjugated diene polymer, and (c) from a (meth) acrylic acid ester monomer
  • a copolymer binder comprising at least one unit selected from the group consisting of derived units, and (D) units derived from water-soluble polymers, wherein the copolymer binder has a wet modulus of at least 0.02 MPa. It provides a binder composition for secondary batteries.
  • the present invention provides a negative electrode for a lithium secondary battery comprising the silicon-based negative electrode active material and the secondary battery binder composition in order to solve the other problem.
  • the present invention provides a lithium secondary battery comprising the electrode for a lithium secondary battery, in order to solve the another problem.
  • the binder composition for a secondary battery according to the present invention includes a copolymer binder including a hydrophilic functional group, and because the copolymer binder has a wet modulus of a predetermined value or more, the copolymer binder exhibits improved adhesion and In addition, high mechanical properties can be maintained even after the electrolyte is impregnated to improve the life performance of the battery.
  • Figure 2 is a graph showing the results of measuring the change in the discharge capacity up to 30 cycles in the charge and discharge current density 0.5 C conditions for the lithium secondary batteries prepared in Example 4 and Comparative Examples 3 and 4.
  • Example 4 is a graph showing the results of measuring the change in the discharge capacity of up to 200 cycles in the charge and discharge current density 0.33 C conditions for the lithium secondary batteries prepared in Example 8 and Comparative Example 5.
  • the binder composition for a lithium secondary battery comprises (a) a unit derived from a vinyl monomer, (b) a unit derived from a conjugated diene monomer or a conjugated diene polymer, and (c) a (meth) acrylic acid ester monomer.
  • a copolymer binder comprising at least one unit selected from the group consisting of derived units, and (D) units derived from water-soluble polymers, wherein the copolymer binder has a wet modulus of at least 0.02 MPa. will be.
  • the copolymer binder may have a wet strength of 0.02 MPa or more, specifically 0.1 MPa or more, more specifically 0.3 MPa to 0.5 MPa, and when the copolymer binder has a wet strength in the above range, swelling by an electrolyte solution This may be appropriately suppressed, and the life characteristics of the electrode and the secondary battery including the same may be improved by maintaining appropriate mechanical properties.
  • the wet strength is obtained by impregnating the copolymer binder in a conventional electrolyte solution used as a lithium secondary battery, and then applying a load to the copolymer binder to generate the inside of the copolymer binder through a stress-strain curve. It can be measured by grasping the relationship between tensile strength (Stress) and tensile strain (Strain).
  • the wet strength indicates the strength of the copolymer binder in the state of being impregnated with the electrolyte as in the actual driving environment of the lithium secondary battery, and thus the dry strength of the copolymer binder in the driving environment of the actual lithium secondary battery. Compared with the dry modulus, it has a different meaning from the higher dry strength.
  • the wet strength value of the copolymer binder can be achieved by controlling the content of the hydrophilic functional group of the copolymer binder, and specifically by appropriately adjusting the content of units derived from the (d) water-soluble polymer included in the copolymer binder.
  • the copolymer binder may have an appropriate wet strength value.
  • the copolymer has a total weight of 100 parts by weight based on (a) 1 to 70 parts by weight of units derived from vinyl monomers, (b) 10 to parts by weight of units derived from conjugated diene monomers or conjugated diene polymers. 97 parts by weight, (C) 1 to 30 parts by weight of the unit derived from the (meth) acrylic acid ester monomer, and (D) 1 to 70 parts by weight of the unit derived from the water-soluble polymer.
  • the copolymer may be based on a total weight of 100 parts by weight of (a) 20 parts by weight to 70 parts by weight of a unit derived from a vinyl monomer, (b) a unit derived from a conjugated diene monomer or a conjugated diene polymer. 10 parts by weight to 60 parts by weight, (c) 1 part by weight to 20 parts by weight of a unit derived from a (meth) acrylic acid ester monomer, and (d) 1 part by weight to 60 parts by weight of a unit derived from a water-soluble polymer. have.
  • the copolymer may be derived from (a) 30 parts by weight to 60 parts by weight of a unit derived from a vinyl monomer, (b) a conjugated diene monomer or a conjugated diene polymer based on a total weight of 100 parts by weight. 15 to 30 parts by weight of the unit, (c) 4 to 8 parts by weight of the unit derived from the (meth) acrylic acid ester monomer, and (d) 2 to 50 parts by weight of the unit derived from the water-soluble polymer.
  • a) 30 parts by weight to 60 parts by weight of a unit derived from a vinyl monomer a conjugated diene monomer or a conjugated diene polymer based on a total weight of 100 parts by weight. 15 to 30 parts by weight of the unit, (c) 4 to 8 parts by weight of the unit derived from the (meth) acrylic acid ester monomer, and (d) 2 to 50 parts by weight of the unit derived from the water-soluble polymer.
  • the copolymer is a unit derived from the (a) vinyl monomer, (b) a unit derived from a conjugated diene monomer or a conjugated diene polymer, and (c) a unit derived from a (meth) acrylic acid ester monomer.
  • the copolymer binder can exhibit excellent adhesion and strength.
  • the copolymer binder may have an excellent wet strength value.
  • the copolymer binder may have a particle shape and have an average particle diameter (D 50 ) of 100 nm to 1 ⁇ m, specifically 300 nm to 500 nm.
  • the copolymer binder has the average particle diameter (D 50 ), it can exhibit an appropriate adhesion, the electrolyte swelling phenomenon is small, and exhibits the proper elasticity to accommodate the change in the thickness of the electrode and reduce the gas generation phenomenon have.
  • the average particle diameter (D 50 ) can be defined as the particle size at 50% of the particle size distribution.
  • the average particle diameter is not particularly limited, but may be measured using, for example, a laser diffraction method or a scanning electron microscope (SEM) photograph.
  • the laser diffraction method can measure a particle diameter of about several mm from the submicron region, and a result having high reproducibility and high resolution can be obtained.
  • the units contained in the copolymer binder are as follows.
  • the vinyl monomer may be at least one selected from the group consisting of styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-t-butylstyrene, and divinylbenzene.
  • the conjugated diene monomer is 1,3-butadiene, isoprene, chloroprene or piperylene
  • the conjugated diene polymer is 1,3- Polymers of two or more monomers selected from the group consisting of butadiene, isoprene, chloroprene, and piperylene, styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, styrene-isoprene copolymers, acrylate-butadiene rubbers, acrylo Nitrile-butadiene-styrene rubber, ethylene-propylene-diene based polymers, and these may be at least one selected from the group consisting of partially hydrogenated, epoxidized, or brominated polymers.
  • the (c) (meth) acrylic acid ester monomers are methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate.
  • the water-soluble polymer is a unit derived from a (meth) acrylic acid ester monomer, a unit derived from a (meth) acryl amide monomer, an unsaturated carboxylic acid monomer and a vinyl acetate monomer. It may be a copolymer including one or more units selected from the group consisting of derived units, and the production method is not particularly limited, but may be prepared according to, for example, suspension polymerization, emulsion polymerization, seed polymerization, or the like.
  • the (meth) acrylic acid ester monomer is methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n- amyl acrylate, iso amyl acrylate, n- Ethylhexyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl Methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, n-ethylhexyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl
  • the (meth) acryl amide monomer is a group consisting of acryl amide, n-methylol acrylamide, n-butoxy methylacrylamide, methacrylamide, n-methylol methacrylamide, n-butoxy methyl methacrylamide It may be one or more selected from.
  • the unsaturated carboxylic acid monomer may be at least one selected from the group consisting of maleic acid, fumaric acid, methacrylic acid, acrylic acid, glutaric acid, itaconic acid, tetrahydrophthalic acid, crotonic acid, isocrotonic acid and nadic acid.
  • the water-soluble polymer may be at least one selected from the group consisting of polyvinyl alcohol (PVA), polyacrylic acid (PAA), and polyacrylamide (PAM), and more specifically, polyacrylic acid (PAA).
  • PVA polyvinyl alcohol
  • PAA polyacrylic acid
  • PAM polyacrylamide
  • the copolymer binder is not particularly limited, but may be prepared by, for example, suspension polymerization, emulsion polymerization, seed polymerization, or the like, and specifically, may be prepared by emulsion polymerization.
  • the copolymer binder may include one or more other components such as a polymerization initiator, a crosslinking agent, a buffer, a molecular weight modifier, an emulsifier, and the like as necessary.
  • the vinyl-based monomer, the conjugated diene-based monomer or the conjugated diene-based may be added thereto, prepared by emulsion polymerization using the water-soluble polymer and the crosslinking agent.
  • the particle size of the copolymer binder may be adjusted according to the content of the emulsifier, and in particular, when the content of the emulsifier is increased, the average particle size of the particles may be reduced, and when the content of the emulsifier is decreased, the average particle size of the particles is greatly increased. can do.
  • the polymerization temperature and the polymerization time may be appropriately determined according to the kind of polymerization method polymerization initiator, etc., for example, the polymerization temperature may be 50 ° C to 300 ° C, and the polymerization time may be 1 hour to 20 hours, but is not particularly limited.
  • Inorganic or organic peroxides may be used as the polymerization initiator, and for example, water-soluble initiators including potassium persulfate, sodium persulfate, ammonium persulfate, and the like, or oil-soluble initiators including cumene hydroperoxide, benzoyl peroxide, and the like. Can be.
  • an activator may be used together to promote the initiation reaction of the polymerization initiator, the activator is selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate and dextrose 1 or more types are mentioned.
  • the crosslinking agent may be used to promote crosslinking of the binder, for example, amines such as diethylenetriamine, triethylene tetraamine, diethylamino propylamine, xylene diamine, isophorone diamine, dodecyl succinic anhydride acid anhydrides such as dodecyl succinic anhydride, phthalic anhydride, polyamide resins, polysulfide resins, phenol resins, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylol propane trimethacrylate, trimethylol methane triacrylate, glycidyl meta Acrylates and the like.
  • the grafting agent may be used together, such as aryl methacryl
  • buffer examples include NaHCO 3 , NaOH, or NH 4 OH.
  • molecular weight regulator examples include mercaptans, terpins such as terbinolene, dipentene, t-terpyene, and halogenated hydrocarbons such as chloroform and carbon tetrachloride.
  • the emulsifier may be an anionic emulsifier, a nonionic emulsifier, or a mixture thereof, and when the nonionic emulsifier is used in combination with the anionic emulsifier, in addition to the electrostatic stabilization of the anionic emulsifier, the colloidal form may be formed through the van der Waals force of the polymer particles. It may provide additional stabilization.
  • anionic emulsifier examples include phosphate, carboxylate, sulfate, succinate, sulfosuccinate, sulfonate, or disulfonate emulsifiers.
  • nonionic emulsifiers include ester type, ether type, and ester-ether type emulsifiers, and although not particularly limited, polyoxyethylene glycol, polyoxyethylene glycol methyl ether, polyoxyethylene monoallyl ether, poly Oxyethylene bisphenol-A ether, polypropylene glycol, polyoxyethylene neopentyl ether, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethyl oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene decyl Ether and polyoxyethylene octyl ether.
  • the secondary battery binder composition may be used as a binder in the production of a lithium secondary battery electrode, and particularly useful when a silicon-based negative electrode active material is used as the negative electrode active material.
  • the present invention provides a negative electrode for a lithium secondary battery including the silicon-based negative active material and the binder composition for the secondary battery.
  • the silicon-based negative active material for example, a group consisting of Si, silicon oxide particles (SiO x , 0 ⁇ x ⁇ 2), Si-metal alloy, and an alloy of Si and silicon oxide particles (SiO x , 0 ⁇ x ⁇ 2) It may include one or more selected from the above, the silicon oxide particles (SiO x , 0 ⁇ x ⁇ 2) may be a composite composed of crystalline SiO 2 and amorphous Si.
  • a carbon material, lithium metal, tin, or the like, which may normally occlude and release lithium ions may be used.
  • a carbon material may be used, and as the carbon material, both low crystalline carbon and high crystalline carbon may be used.
  • Soft crystalline carbon and hard carbon are typical low crystalline carbon, and high crystalline carbon is natural graphite, kish graphite, pyrolytic carbon, liquid crystal pitch carbon fiber.
  • High-temperature calcined carbon such as (mesophase pitch based carbon fiber), meso-carbon microbeads, mesophase pitches and petroleum or coal tar pitch derived cokes.
  • the negative electrode for a lithium secondary battery may further include a carbon-based negative electrode active material, wherein the silicon-based negative electrode active material is 1% to 30% by weight of the total negative electrode active material, specifically 5 wt% to 10 wt% may be included.
  • the carbon-based negative electrode active material may be natural graphite, artificial graphite, or a mixture thereof.
  • the secondary battery binder used to form the negative electrode active material layer of the negative electrode has a wetness of 0.02 MPa or more, specifically 0.1 MPa or more, more specifically 0.3 MPa to 0.5 MPa.
  • a wetness 0.02 MPa or more, specifically 0.1 MPa or more, more specifically 0.3 MPa to 0.5 MPa.
  • the lithium secondary battery may include a separator interposed between the negative electrode, the positive electrode, and the negative electrode and the positive electrode.
  • the negative electrode may be manufactured by a conventional method known in the art, and for example, a negative electrode active material slurry is prepared by mixing and stirring additives such as the negative electrode active material, the above-described binder, and a conductive material, and then apply the negative electrode active material to the negative electrode current collector. It can be prepared by drying and compressing.
  • the solvent for forming the negative electrode includes an organic solvent such as NMP (N-methyl pyrrolidone), DMF (dimethyl formamide), acetone, dimethyl acetamide or water, and these solvents alone or in combination of two or more. Can be mixed and used. The amount of the solvent used is sufficient to dissolve and disperse the negative electrode active material, the binder, and the conductive material in consideration of the coating thickness of the slurry and the production yield.
  • NMP N-methyl pyrrolidone
  • DMF dimethyl formamide
  • acetone dimethyl acetamide or water
  • the secondary battery binder composition may be included in less than 10% by weight of the total weight of the slurry for the negative electrode active material, specifically 0.1 to 10% by weight, more specifically 0.5 to 4% by weight may be included. If the content of the binder is less than 0.1% by weight, the effect of using the binder is insignificant and undesirable. If the content of the binder exceeds 10% by weight, the capacity per volume may decrease due to the decrease in the relative content of the active material due to the increase in the content of the binder. Not desirable
  • the conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • Examples of the conductive material include graphite such as natural graphite and artificial graphite; Carbon blacks such as acetylene black, Ketjen black, channel black, furnace black, lamp black and thermal black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskers such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Or conductive materials such as polyphenylene derivatives.
  • the conductive material may be used in an amount of 1% by weight to 9% by weight based on the total weight of the slurry for the negative electrode active material.
  • the negative electrode current collector used for the negative electrode according to an embodiment of the present invention may have a thickness of 3 ⁇ m to 500 ⁇ m.
  • the negative electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • the negative electrode current collector may be formed on the surface of copper, gold, 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.
  • fine concavities and convexities may be formed on the surface to enhance the bonding strength of the negative electrode active material, and may be used in various forms such as films, sheets, foils, nets, porous bodies, foams, and nonwoven fabrics.
  • the active material slurry may include a viscosity modifier and / or fillers as needed.
  • the viscosity adjusting agent may be carboxymethyl cellulose, polyacrylic acid, or the like, and the viscosity of the active material slurry may be adjusted to facilitate the preparation of the active material slurry and the coating process on the electrode current collector by addition.
  • the filler is an auxiliary component that suppresses the expansion of the electrode, and is not particularly limited as long as it is a fibrous material that does not cause chemical change in the battery.
  • the filler is fibrous such as olefin-based polymers such as polyethylene and polypropylene, glass fibers, and carbon fibers. It may be a substance.
  • the positive electrode can be prepared by conventional methods known in the art.
  • a slurry may be prepared by mixing and stirring a solvent, the above-described binder, a conductive material, and a dispersant in a positive electrode active material, and then applying the coating (coating) to a current collector of a metal material, compressing it, and drying the same to prepare a positive electrode.
  • the current collector of the metal material is a metal having high conductivity, and is a metal to which the slurry of the positive electrode active material can be easily adhered, and is particularly limited as long as it has high conductivity without causing chemical change in the battery in the voltage range of the battery.
  • surface treated with carbon, nickel, titanium, silver, or the like on the surface of stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel may be used.
  • fine unevenness may be formed on the surface of the current collector to increase the adhesion of the positive electrode active material.
  • the current collector may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven fabric, and may have a thickness of 3 to 500 ⁇ m.
  • the solvent for forming the positive electrode includes an organic solvent such as NMP (N-methyl pyrrolidone), DMF (dimethyl formamide), acetone, dimethyl acetamide or water, and these solvents alone or in combination of two or more. Can be mixed and used. The amount of the solvent used is sufficient to dissolve and disperse the positive electrode active material, the binder, and the conductive material in consideration of the coating thickness of the slurry and the production yield.
  • NMP N-methyl pyrrolidone
  • DMF dimethyl formamide
  • acetone dimethyl acetamide or water
  • the conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • Examples of the conductive material include graphite such as natural graphite and artificial graphite; Carbon blacks such as acetylene black, Ketjen black, channel black, farnes black, lamp black and thermal black; Conductive fibers such as carbon fibers and metal fibers; Conductive tubes such as carbon nanotubes; Metal powders such as fluorocarbon, aluminum and nickel powders; Conductive whiskers such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • the conductive material may be used in an amount of 1 wt% to 20 wt% with respect to the total weight of the positive electrode slurry.
  • the dispersant may be an aqueous dispersant or an organic dispersant such as N-methyl-2-pyrrolidone.
  • separator conventional porous polymer films conventionally used as separators, such as polyolefin-based polymers such as ethylene homopolymer, propylene homopolymer, ethylene-butene copolymer, ethylene-hexene copolymer and ethylene-methacrylate copolymer
  • the porous polymer film prepared by using a single or a lamination thereof may be used, or a conventional porous nonwoven fabric, such as a high melting point glass fiber, polyethylene terephthalate fiber, etc. may be used, but is not limited thereto.
  • organic solvent included in the electrolyte solution those conventionally used in the electrolyte for secondary batteries may be used without limitation, and typically propylene carbonate (PC), ethylene carbonate (ethylene carbonate, EC ), Diethyl carbonate (DEC), dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), methylpropyl carbonate, dipropyl carbonate, dimethyl sulfoxide, acetonitrile, dimethoxyethane, diethoxyethane , Vinylene carbonate, sulfolane, gamma-butyrolactone, propylene sulfite, tetrahydrofuran, any one selected from the group consisting of, or mixtures of two or more thereof may be representatively used.
  • PC propylene carbonate
  • EC ethylene carbonate
  • DEC Diethyl carbonate
  • DMC dimethyl carbonate
  • EMC ethylmethyl carbonate
  • methylpropyl carbonate dipropyl carbon
  • ethylene carbonate and propylene carbonate which are cyclic carbonates among the carbonate-based organic solvents, may be preferably used because they have high dielectric constants to dissociate lithium salts in the electrolyte, and may be preferably used in such cyclic carbonates.
  • a low viscosity, low dielectric constant linear carbonate such as ethyl carbonate is mixed and used in an appropriate ratio, an electrolyte having high electrical conductivity can be prepared, and thus it can be used more preferably.
  • the electrolyte solution stored according to the present invention may further include additives such as an overcharge inhibitor included in a conventional electrolyte solution.
  • 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.
  • a copolymer binder having an average particle diameter (D 50 ) of 350 nm was obtained in the same manner as in Example 1, except that polyacrylic acid was used in an amount of 42 g.
  • a copolymer binder having an average particle diameter (D 50 ) of 450 nm was obtained in the same manner as in Example 1, except that polyacrylic acid was used in an amount of 98 g.
  • a copolymer binder having an average particle diameter (D 50 ) of 200 nm was obtained in the same manner as in Comparative Example 1, except that 1,3-butadiene and butyl acrylate were changed to the amounts of 50 g and 10 g, respectively. .
  • Artificial graphite natural graphite: silicon-based negative electrode active material (SiO) mixed in a weight ratio of 84.5: 10.5: 5 mixed negative electrode active material, a thickener (carboxy methyl cellulose), carbon black as a conductive material, the binder prepared in Example 2 98
  • a negative electrode slurry was prepared by mixing using a TK mixer at a weight ratio of 1: 1: 2. The negative electrode slurry was coated on a copper foil of 20 ⁇ m to a thickness of 120 ⁇ m, dried at 100 ° C. for 12 hours in a vacuum oven, and then rolled to a suitable thickness to prepare a negative electrode.
  • 96 g of LiCoO 2 , 2 g of acetylene black, and 2 g of polyvinylidene fluoride (PVdF) as a positive electrode active material were added to N-methyl-2-pyrrolidone (NMP) as a solvent to prepare a slurry for the positive electrode.
  • NMP N-methyl-2-pyrrolidone
  • the anode slurry was coated on an aluminum (Al) thin film to a thickness of 350 ⁇ m, dried to prepare a cathode, and then roll-rolled to prepare a cathode.
  • the anode prepared above was punched out to have a surface area of 13.33 cm 2 , and the anode prepared above was punched out to have a surface area of 12.60 cm 2 to prepare a mono-cell.
  • a tap was attached to the upper part of the positive electrode and the negative electrode, and the resultant was loaded into an aluminum pouch through a separator made of a polyolefin microporous membrane between the negative electrode and the positive electrode, and 500 mg of the electrolyte was injected into the pouch.
  • the pouch was sealed using a vacuum packaging machine and maintained at room temperature for 12 hours, followed by a constant current charging process to maintain a constant current at a rate of about 0.05 C and maintain a voltage until about 1/6 of the current. .
  • a constant current charging process to maintain a constant current at a rate of about 0.05 C and maintain a voltage until about 1/6 of the current.
  • Example 4 Except that the copolymer binder of Example 1 was used as the binder in the preparation of the negative electrode in Example 4, and the artificial negative electrode: natural graphite: silicon-based negative active material was mixed mixed active material in a weight ratio of 80:10:10. Through the same process as in Example 4, a negative electrode, a positive electrode, and a lithium secondary battery were prepared.
  • Example 4 Preparation of the negative electrode in Example 4
  • the artificial graphite natural graphite: silicon-based negative electrode active material using a mixed negative electrode active material mixed in a weight ratio of 80:10:10, and using the copolymer binder of Examples 2 and 3, respectively Except, a negative electrode, a positive electrode and a lithium secondary battery were prepared through the same process as in Example 4.
  • Example 4 except that the artificial graphite: silicone-based negative active material was mixed in a weight ratio of 70:30 and the copolymer binder of Example 3 was used to prepare the negative electrode in Example 4, Through the same process as to prepare a negative electrode, a positive electrode and a lithium secondary battery.
  • a negative electrode, a positive electrode and a lithium secondary battery were manufactured through the same process as in Example 4, except that the copolymer binders prepared in Comparative Examples 1 and 2 were used as binders in preparing the negative electrode in Example 4. .
  • Example 4 Except that the artificial graphite: silicone-based negative active material was mixed in a weight ratio of 70:30, and the copolymer binder prepared in Comparative Example 1 was used in the preparation of the negative electrode in Example 4, A negative electrode, a positive electrode, and a lithium secondary battery were manufactured through the same process as in Example 4.
  • the charge and discharge current density was 0.5 C
  • the charge end voltage was 4.2 V (Li / Li + )
  • the discharge end voltage was 3 V (Li / Charge and discharge tests with Li + ) were performed 30 times.
  • the charging and discharging current density was 1 C
  • the charging end voltage was 4.2 V (Li / Li + )
  • the discharge end voltage was 3 V (Li / Li + ). Charge and discharge tests were performed 130 times.
  • the charge and discharge current density was 0.33 C
  • the charge end voltage was 4.2 V (Li / Li + )
  • the discharge end voltage was 3 V (Li / Li + ). 200 charge and discharge tests were conducted.
  • the copolymer binders of Comparative Examples 1 and 2 having low wet strength were significantly swelled by the electrolyte solution compared to the copolymer binder of Example 2 having high wet strength ( swelling).
  • the negative electrode and the secondary battery of Comparative Examples 3 and 4 prepared using the same have poor capacity retention compared to the negative electrode and the secondary battery of Example 4 prepared using the copolymer binder of Example 2.
  • Figure 3 can be confirmed the capacity retention rate of the secondary battery according to the wet strength of the copolymer binder used. Referring to FIG.
  • Figure 4 shows the experimental results for comparing the difference in effect according to the type of the copolymer binder when the negative electrode was prepared using a negative electrode active material mixed with artificial graphite and a silicon-based negative active material in a weight ratio of 70:30 have.
  • the negative electrode and the secondary battery of Example 4 including the copolymer binder of Example 3 exhibit excellent capacity retention ratios compared to the negative electrode and the secondary battery of Comparative Example 5 including the copolymer binder of Comparative Example 1. It can be confirmed that.
  • the copolymer binder of the present invention having a wet strength of 0.02 MPa or more is applied to a negative electrode including a silicon-based negative active material having a large volume change due to charging and discharging, the copolymer binder exhibits improved adhesion and high mechanical strength. Since physical properties were maintained, it was confirmed that the life performance of the secondary battery could be improved.

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Abstract

La présente invention concerne une composition de liant pour une batterie secondaire, ainsi qu'une anode de batterie secondaire au lithium et une batterie secondaire au lithium comprenant la composition de liant, la composition de liant comprenant un liant copolymère comprenant (a) une unité dérivée d'un monomère à base de vinyle, (b) une unité dérivée d'un monomère à base de diène conjugué ou d'un polymère à base de diène conjugué, (c) au moins une unité choisie dans le groupe constitué par les unités dérivées d'un monomère à base d'ester d'acide (méth)acrylique et (d) une unité dérivée d'un polymère hydrosoluble, le liant copolymère ayant un module humide supérieur ou égal à 0,02 MPa.
PCT/KR2018/003746 2017-03-31 2018-03-29 Composition de liant pour batterie secondaire, électrode pour batterie secondaire et batterie secondaire au lithium comprenant celle-ci WO2018182343A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US16/325,500 US11024851B2 (en) 2017-03-31 2018-03-29 Binder composition for secondary battery, and electrode for secondary battery and lithium secondary battery which include the same
PL18776291T PL3483964T3 (pl) 2017-03-31 2018-03-29 Kompozycja środka wiążącego dla akumulatora i elektroda dla akumulatora oraz akumulator litowy, który ją zawiera
CN201880003405.7A CN109716566B (zh) 2017-03-31 2018-03-29 二次电池用粘合剂组合物以及包含其的二次电池用电极和锂二次电池
EP18776291.9A EP3483964B1 (fr) 2017-03-31 2018-03-29 Composition de liant pour batterie secondaire, électrode pour batterie secondaire et batterie secondaire au lithium comprenant celle-ci
JP2019548849A JP7034407B2 (ja) 2017-03-31 2018-03-29 二次電池用バインダー組成物、それを含む二次電池用電極、およびリチウム二次電池

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KR20170042131 2017-03-31
KR10-2017-0042131 2017-03-31
KR1020180035834A KR102290957B1 (ko) 2017-03-31 2018-03-28 이차전지용 바인더 조성물, 이를 포함하는 이차전지용 전극 및 리튬 이차전지
KR10-2018-0035834 2018-03-28

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CN114243022A (zh) * 2022-02-24 2022-03-25 北京壹金新能源科技有限公司 一种锂离子电池用三维网络水系粘结剂、制备及其应用
US20230141592A1 (en) * 2020-06-17 2023-05-11 Grst International Limited Binder composition for secondary battery
KR20230087590A (ko) 2020-12-15 2023-06-16 아사히 가세이 가부시키가이샤 비수계 이차 전지용 중합체 조성물 및 비수계 이차 전지
CN116376481A (zh) * 2023-06-05 2023-07-04 宁德时代新能源科技股份有限公司 负极粘结剂、负极极片、电池单体、电池和用电装置
KR20240088962A (ko) 2021-10-29 2024-06-20 니폰 제온 가부시키가이샤 비수계 이차 전지 부극용 바인더 조성물, 비수계 이차 전지 부극용 슬러리 조성물, 비수계 이차 전지용 부극, 및 비수계 이차 전지

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Publication number Priority date Publication date Assignee Title
US20230141592A1 (en) * 2020-06-17 2023-05-11 Grst International Limited Binder composition for secondary battery
KR20230087590A (ko) 2020-12-15 2023-06-16 아사히 가세이 가부시키가이샤 비수계 이차 전지용 중합체 조성물 및 비수계 이차 전지
KR20240088962A (ko) 2021-10-29 2024-06-20 니폰 제온 가부시키가이샤 비수계 이차 전지 부극용 바인더 조성물, 비수계 이차 전지 부극용 슬러리 조성물, 비수계 이차 전지용 부극, 및 비수계 이차 전지
CN114243022A (zh) * 2022-02-24 2022-03-25 北京壹金新能源科技有限公司 一种锂离子电池用三维网络水系粘结剂、制备及其应用
CN114243022B (zh) * 2022-02-24 2022-04-29 北京壹金新能源科技有限公司 一种锂离子电池用三维网络水系粘结剂、制备及其应用
CN116376481A (zh) * 2023-06-05 2023-07-04 宁德时代新能源科技股份有限公司 负极粘结剂、负极极片、电池单体、电池和用电装置
CN116376481B (zh) * 2023-06-05 2023-10-27 宁德时代新能源科技股份有限公司 负极粘结剂、负极极片、电池单体、电池和用电装置

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