WO2022086173A1 - 이차 전지의 음극용 바인더, 이차 전지의 음극 및 이차 전지 - Google Patents
이차 전지의 음극용 바인더, 이차 전지의 음극 및 이차 전지 Download PDFInfo
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- WO2022086173A1 WO2022086173A1 PCT/KR2021/014716 KR2021014716W WO2022086173A1 WO 2022086173 A1 WO2022086173 A1 WO 2022086173A1 KR 2021014716 W KR2021014716 W KR 2021014716W WO 2022086173 A1 WO2022086173 A1 WO 2022086173A1
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- Prior art keywords
- monomer
- negative electrode
- binder
- secondary battery
- acid
- Prior art date
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a binder for a negative electrode of a secondary battery, a negative electrode for a secondary battery, and a secondary battery.
- the field of application of secondary batteries is expanding from portable electronic devices to medium and large-sized devices such as hybrid vehicles and electric vehicles.
- the negative electrode of the secondary battery includes a current collector and a negative electrode active material layer, wherein the negative electrode active material layer includes a negative electrode active material and a binder.
- the negative electrode active material various types of carbon-based materials including artificial, natural graphite, and hard carbon capable of insertion/desorption of lithium have been applied, and silicon, tin, silicon-tin alloy, etc. Research to use it as an active material is also ongoing.
- the secondary battery has a problem in that stability and lifespan decrease as charging and discharging are repeated. Specifically, the volume of the negative active material expands and contracts according to repeated charging and discharging of the secondary battery, and in this process, the binding force of the binder binding the negative active material and the current collector may be reduced. Such a problem is exacerbated as the discharge capacity of the anode active material increases.
- the binder of the negative electrode may expand according to the impregnation of the electrolyte, thereby reducing the binding force of the binder.
- the present invention is to minimize the volume change of the negative electrode and the secondary battery by improving the binder applied to the negative electrode of the secondary battery, while increasing the energy density, to minimize the decrease in capacity.
- a binder for a negative electrode of a secondary battery including binder particles having an isoprene-based core and a butadiene-based shell structure.
- a method of manufacturing a binder for a negative electrode of a secondary battery in which an isoprene-based core is synthesized and a butadiene-based shell is formed in a continuous process.
- a negative electrode mixture in another embodiment, there is provided a negative electrode mixture, a negative electrode, and a secondary battery including the binder for the negative electrode of the above-described embodiment.
- the binder for the negative electrode of the one embodiment the electrolyte impregnation rate is low, volume expansion is suppressed, together with an isoprene-based core that can improve the life of the secondary battery;
- an isoprene-based core that can improve the life of the secondary battery;
- a butadiene-based shell that has excellent adhesion and can maintain binding force between the anode active material and the current collector even by repeated charging and discharging, it is possible to ultimately secure the stability and lifespan of the secondary battery.
- each layer or element when each layer or element is referred to as being formed “on” or “over” each layer or element, it means that each layer or element is formed directly on the respective layers or elements, or that each layer or element is formed directly on another layer or element. This means that elements may additionally be formed between each layer, on the object, on the substrate.
- copolymerization may mean block copolymerization, random copolymerization, graft copolymerization or alternating copolymerization
- copolymer means block copolymer, random copolymer, graft copolymer or alternating copolymer. It can mean amalgamation.
- a binder for a negative electrode of a secondary battery comprising binder particles having a core-shell structure.
- the binder for the negative electrode of the embodiment may take both the advantage of the core particle and the advantage of the shell.
- the binder particles having the core-shell structure may include: copolymer core particles including repeating units derived from isoprene-based monomers; and a copolymer shell located on the surface of the core particle and including a butadiene-based monomer-derived repeating unit.
- the binder for the negative electrode of one embodiment may be made of only the binder particles having the core-shell structure as a solid content, or may be implemented in the form of a composition to which an aqueous solvent is added.
- the core particles include (a) a first repeating unit derived from an isoprene-based first monomer, (b) a second repeating unit derived from an aromatic vinyl-based second monomer, and (c) a third repeating unit derived from a third unsaturated carboxylic acid-based monomer. It may be a copolymer comprising
- the first repeating unit is derived from the isoprene-based first monomer. Specifically, the first repeating unit corresponds to a structural unit of a copolymer formed from the isoprene-based first monomer supplied during the synthesis of the core particle.
- the binder including the first repeating unit suppresses electrolyte impregnation and volume expansion, and may improve the lifespan of the secondary battery.
- the first monomer may be isoprene.
- the second repeating unit is derived from an aromatic vinyl-based second monomer. Specifically, the second repeating unit corresponds to a structural unit of the copolymer formed from the aromatic vinyl-based second monomer supplied during the synthesis of the core particle.
- the strength of the binder including the second repeating unit and affinity with the electrolyte may be improved.
- the aromatic vinyl-based second monomer is styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-t-butylstyrene, chlorostyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylnaphthalene, chloromethylstyrene, hydroxymethylstyrene, and It may be at least one selected from the group consisting of divinylbenzene, for example, may be styrene.
- the third repeating unit is derived from an unsaturated carboxylic acid-based third monomer. Specifically, the third repeating unit corresponds to a structural unit of the copolymer formed from the third monomer supplied during the synthesis of the core particle.
- the binder including the third repeating unit may have improved strength, polymerization stability, and storage stability.
- the unsaturated carboxylic acid-based third monomer is 1 selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, glutaric acid, itaconic acid, tetrahydrophthalic acid, crotonic acid, isocrotonic acid, and nadic acid may be more than one species.
- it may be acrylic acid and itaconic acid.
- a) 30 to 65 wt% of a first repeating unit derived from an isoprene-based first monomer, (b) 30 to 65 wt% of a second repeating unit derived from an aromatic vinyl-based second monomer And (c) 0.1 to 10% by weight of a third repeating unit derived from an unsaturated carboxylic acid-based third monomer may be included.
- the effects of the first to third repeating units may be harmonized.
- the first repeating unit derived from the isoprene-based first monomer is 30 wt% or more, 32 wt% or more, 34 wt% or more, or 36 wt% As included above, 65% by weight or less, 62% by weight or less, 59% by weight or less, or 56% by weight or less may be included.
- the second repeating unit derived from the aromatic vinyl-based second monomer is 30% by weight or more, 32% by weight or more, 34% by weight or more, or 36% by weight or more.
- 65 wt% or less, 62 wt% or less, 59 wt% or less, or 56 wt% or less may be included.
- the third repeating unit derived from the unsaturated carboxylic acid-based third monomer is 0.1 wt% or more, 0.5 wt% or more, 1 wt% or more, or 3 wt% or more As included as, it may be included in an amount of 10% by weight or less, 9% by weight or less, 8% by weight or less, or 7% by weight or less.
- the shell includes (d) a fourth repeating unit derived from a fourth butadiene-based monomer, (e) a fifth repeating unit derived from an aromatic vinyl-based fifth monomer, and (f) a sixth repeating unit derived from a sixth unsaturated carboxylic acid-based monomer. It may be a copolymer.
- the fourth repeating unit is derived from a fourth butadiene-based monomer. Specifically, the fourth repeating unit corresponds to a structural unit of a copolymer formed from the isoprene-based fourth monomer supplied during the synthesis of the core particle.
- the binder including the fourth repeating unit has excellent adhesion, so that the binding force between the negative active material and the current collector can be maintained even by repeated charging and discharging.
- the fourth monomer may be 1,3-butadiene.
- the fifth repeating unit is derived from an aromatic vinyl-based fifth monomer.
- the fifth repeating unit corresponds to a structural unit of a copolymer formed from the fifth aromatic vinyl-based monomer supplied during the synthesis of the shell.
- the strength of the binder including the fifth repeating unit and affinity with the electrolyte may be improved.
- the aromatic vinyl-based fifth monomer is styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-t-butylstyrene, chlorostyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylnaphthalene, chloromethylstyrene, hydroxymethylstyrene, and It may be at least one selected from the group consisting of divinylbenzene, for example, may be styrene.
- the sixth repeating unit is derived from a sixth unsaturated carboxylic acid-based monomer. Specifically, the sixth repeating unit corresponds to a structural unit of the copolymer formed from the sixth monomer supplied during the synthesis of the core particle.
- the binder including the sixth repeating unit may have improved strength, polymerization stability, and storage stability.
- the unsaturated carboxylic acid-based sixth monomer is 1 selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, glutaric acid, itaconic acid, tetrahydrophthalic acid, crotonic acid, isocrotonic acid, and nadic acid may be more than one species.
- it may be acrylic acid and itaconic acid.
- the shell Of the total amount (100 wt%) of the shell, (d) 30 to 85 wt% of the fourth repeating unit derived from the fourth butadiene-based monomer, (e) 10 to 65 wt% of the fifth repeating unit derived from the fifth aromatic vinyl-based monomer, and (f) 0.1 to 15% by weight of the sixth repeating unit derived from the sixth unsaturated carboxylic acid-based monomer may be included.
- the fourth repeating unit derived from the butadiene-based fourth monomer is 30% by weight or more, 32% by weight or more, 34% by weight or more, or 36% by weight or more.
- 85 wt% or less, 82 wt% or less, 78 wt% or less, or 75 wt% or less may be included.
- the second repeating unit derived from the fifth aromatic vinyl monomer is 10% by weight or more, 12% by weight or more, 14% by weight or more, or 16% by weight or more.
- 65 wt% or less, 62 wt% or less, 59 wt% or less, or 56 wt% or less may be included.
- the sixth repeating unit derived from the unsaturated carboxylic acid-based sixth monomer is 0.1% by weight or more, 0.5% by weight or more, 1% by weight or more, or 3% by weight or more. , 15 wt% or less, 13 wt% or less, 11 wt% or less, or 9 wt% or less.
- the weight ratio (core:shell) of the core particle and the shell is 1:1 to 15:1, specifically 2:1 to 14:1, more specifically 3:1 to 13:1, such as 4:1 to 12:1.
- the isoprene-based core capable of improving the lifespan of the secondary battery
- a butadiene-based shell that has excellent adhesion and can maintain the binding force between the negative electrode active material and the current collector even by repeated charging and discharging
- the binder particles having the core-shell structure may be manufactured through continuous emulsion polymerization and may have a latex particle shape.
- the binder particles of the core-shell structure may be latex particles having an average particle diameter of 90 to 500 nm.
- the average particle diameter of the latex particles may be measured using a particle size analyzer (NICOMP AW380, manufactured by PSS) using dynamic light scattering.
- NICOMP AW380 manufactured by PSS
- the 'average particle diameter' means an arithmetic average particle diameter in a particle size distribution measured by dynamic light scattering, wherein the arithmetic average particle diameter is the scattering intensity average particle diameter, It can be measured by the average particle diameter of volume distribution or the average particle diameter of number distribution, and it is preferable to measure the average particle diameter of scattering intensity among them.
- the core-shell structure of the binder particles is 90 nm or more, 120 nm or more, 150 nm or more, or 170 nm or more, and 500 nm or less, or 400 nm or less, or 300 nm or less, or 200 nm or less. It may be a latex particle having an average particle diameter.
- the viscosity may increase and the adhesive force of the mixture layer including the same to the current collector may be weakened.
- the average particle diameter of the binder particles having the core-shell structure is too large The stability of the particles may be reduced.
- the binder for the negative electrode of the embodiment may be implemented in the form of a latex composition by further including an aqueous solvent, that is, water together with the binder particles having the core-shell structure.
- the aqueous solvent in terms of stability and viscosity control of the latex particles (the binder particles of the core-shell structure), based on 100 parts by weight of the binder particles of the core-shell structure, from about 50 to about 1,000 parts by weight, specifically about 100 to about 400 parts by weight may be used.
- the total amount (100% by weight) of the binder for the negative electrode of the embodiment it may be used so that the total solid content (TSC) is adjusted to about 10 to about 65%.
- the stability of the latex particles (the binder particles of the core-shell structure) may be deteriorated, and when the solvent is used too much, the viscosity is lowered, and the adhesive strength of the binder is reduced. may be weakened, and thus the overall performance of the battery may be deteriorated.
- a method of manufacturing a binder for a negative electrode of a secondary battery in which an isoprene-based core is synthesized and a butadiene-based shell is formed in a continuous process.
- the manufacturing method of the embodiment comprises the steps of polymerizing a first monomer mixture including an isoprene-based monomer to prepare a copolymer core particle including a repeating unit derived from an isoprene-based monomer; and polymerizing a second monomer mixture including a butadiene-based monomer in the presence of the core particles to form a copolymer shell including a butadiene-based monomer-derived repeating unit on the surface of the core particles; including, as described above
- the binder for the negative electrode of one embodiment can be obtained.
- copolymer core particles including repeating units derived from isoprene-based monomers may be prepared.
- the first monomer mixture may include (a) an isoprene-based first monomer, (b) an aromatic vinyl-based second monomer, and (c) an unsaturated carboxylic acid-based third monomer.
- the content of each monomer in the first monomer mixture may be the same as the content of each repeating unit in the aforementioned core particle, and a detailed description thereof will be omitted.
- a copolymer shell including a butadiene-based monomer-derived repeating unit may be formed on the surface of the core particle.
- the second monomer mixture may include (d) a fourth butadiene-based monomer, (e) an aromatic vinyl-based fifth monomer, and (f) an unsaturated carboxylic acid-based sixth monomer.
- each monomer in the second monomer mixture may be the same as the content of each repeating unit in the shell described above, and a detailed description thereof will be omitted.
- the polymerization of the first monomer mixture and the polymerization of the second monomer mixture may be each independently performed by an emulsion polymerization method.
- each of the above steps may be performed in the presence of an aqueous solvent, an emulsifier and a polymerization initiator.
- the emulsion polymerization may be performed by single polymerization or multi-stage polymerization.
- single polymerization refers to a method in which used monomers are put into a single reactor and polymerized at the same time
- multistage polymerization refers to a method in which used monomers are sequentially polymerized in two or more stages.
- the aqueous solvent is the same as described above, and detailed description thereof is omitted.
- the polymerization temperature and polymerization time of the emulsion polymerization for the preparation of the copolymer may be appropriately determined depending on the case.
- the polymerization temperature may be from about 50 °C to about 200 °C
- the polymerization time may be from about 0.5 hours to about 20 hours.
- an inorganic or organic peroxide may be used, for example, a water-soluble initiator containing potassium persulfate, sodium persulfate, ammonium persulfate, etc., cumene hydroperoxide, benzoyl peroxide Oil-soluble initiators including oxides and the like can be used.
- an activator may be further included to promote the initiation of the reaction of the peroxide together with the polymerization initiator, and such activators include sodium formaldehyde sulfoxylate, sodium ethylenediaminetetraacetate, ferrous sulfate, and dextrose. At least one selected from the group consisting of may be used.
- an anionic emulsifier such as sodium dodecyl diphenyl iser disulfonate, sodium lauryl sulfate, sodium dodecyl benzene sulfonate, dioctyl sodium sulfosuccinate, or polyoxyethylene
- Nonionic emulsifiers such as polyethylene oxide alkyl ethers such as lauryl ether, polyethylene oxide alkyl aryl ethers, polyethylene oxide alkyl amines, and polyethylene oxide alkyl esters may be used.
- Such an emulsifier is a material having a hydrophilic group and a hydrophobic group at the same time, and during the emulsion polymerization process, a micelle structure is formed, and polymerization of each monomer can occur inside the micellar structure.
- the anionic emulsifier and the nonionic emulsifier may be used alone or in a mixture of two or more, and it may be more effective when a mixture of an anionic emulsifier and a nonionic emulsifier is used, but the present invention is not necessarily such an emulsifier is not limited to the type of
- the emulsifier for example, based on 100 parts by weight of the total monomer components used in the preparation of the copolymer, about 0.01 to about 10 parts by weight, about 1 to about 10 parts by weight, or about 3 to about 5 parts by weight can be used as wealth.
- a negative electrode mixture including the binder for the negative electrode and the negative electrode active material of the above-described embodiment, and a negative electrode including a negative electrode mixture layer including the negative electrode mixture and a negative electrode current collector .
- the negative electrode active material used for the negative electrode mixture and the negative electrode, the negative electrode current collector, etc. may each include generally known components.
- the solid content of the negative electrode binder of the embodiment may be included in an amount of 1% to 10% by weight, specifically 1% to 5% by weight. When this is satisfied, the content of the negative active material may be relatively increased, and the discharge capacity of the negative electrode may be further improved.
- the binder for a negative electrode of one embodiment has excellent properties in binding force and mechanical properties, etc.
- a graphite-based negative electrode active material is used as the negative electrode active material of the negative electrode mixture, as well as a negative electrode active material having a higher capacity than that is used, the negative electrode
- the binding force between the active material and the negative electrode active material, between the negative electrode active material and the negative electrode current collector, etc. can be maintained, and expansion of the negative electrode active material can be suppressed by its own mechanical properties.
- the binder for the negative electrode of one embodiment is suitable to be applied not only with the graphite-based negative active material but also with the negative active material having a higher capacity than that, in one embodiment of the present invention, the type of the negative electrode active material is not particularly limited.
- carbon such as non-graphitizable carbon and graphite-based carbon
- Li x Fe 2 O 3 (0 ⁇ x ⁇ 1), Li x WO 2 (0 ⁇ x ⁇ 1), Sn x Me 1-x Me' y O z
- Me metal composite oxides such as Al, B, P, Si, elements of Groups 1, 2, and 3 of the periodic table, halogen; 0 ⁇ x ⁇ 1;1 ⁇ y ⁇ 3;1 ⁇ z ⁇ 8)
- lithium metal lithium alloy; silicon-based alloys; tin-based alloys; SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 O 4 , metal oxides such as Bi 2 O 5 ;
- conductive polymers such as polyacetylene; Li-
- a conductive material, a filler, etc. may be further added to the negative electrode mixture of the embodiment.
- the conductive material is used to impart conductivity to the negative electrode, and any electronically conductive material can be used as long as it does not cause chemical change in the battery configured, for example, natural graphite, artificial graphite, carbon black, acetylene black, ketjen black , carbon-based materials such as carbon fibers; metal-based substances such as metal powders such as copper, nickel, aluminum, and silver, or metal fibers; conductive polymers such as polyphenylene derivatives; Alternatively, a conductive material including a mixture thereof may be used.
- the filler is optionally used as a component for suppressing the expansion of the negative electrode, and is not particularly limited as long as it is a fibrous material without causing a chemical change in the battery.
- a fibrous material such as glass fiber or carbon fiber may be used.
- a secondary battery including the negative electrode of the embodiment described above is provided.
- Such a secondary battery, a positive electrode; electrolyte; and a negative electrode and may be implemented as a lithium secondary battery.
- the lithium secondary battery may be manufactured by impregnating an electrode assembly including a positive electrode, a separator, and a negative electrode with a non-aqueous electrolyte.
- the negative electrode may be prepared by applying the negative electrode mixture according to the above-described embodiment on the negative electrode current collector, followed by drying and rolling.
- the negative electrode current collector is generally made to have a thickness of 3 ⁇ m to 500 ⁇ m.
- Such a negative current collector is not particularly limited as long as it has conductivity without causing a chemical change in the battery.
- the surface of copper, stainless steel, aluminum, nickel, titanium, fired carbon, copper or stainless steel. Carbon, nickel, titanium, silver, etc. surface-treated, aluminum-cadmium alloy, etc. may be used.
- the bonding strength of the negative electrode active material may be strengthened by forming fine irregularities on the surface, and may be used in various forms such as films, sheets, foils, nets, porous bodies, foams, and nonwovens.
- the positive electrode current collector is generally made to have a thickness of 3 ⁇ m to 500 ⁇ m.
- the positive electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery, and for example, stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel. Carbon, nickel, titanium, silver, etc. may be used on the surface of the surface-treated.
- the current collector may increase the adhesion of the positive electrode active material by forming fine irregularities on the surface thereof, and various forms such as a film, sheet, foil, net, porous body, foam body, and non-woven body are possible.
- the conductive material is not particularly limited as long as it has conductivity without causing a chemical change in the battery.
- graphite such as natural graphite or artificial graphite
- carbon black such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and summer black
- conductive fibers such as carbon fibers and metal fibers
- metal powders such as carbon fluoride, aluminum, and nickel powder
- conductive whiskeys such as zinc oxide and potassium titanate
- conductive metal oxides such as titanium oxide
- Conductive materials such as polyphenylene derivatives may be used.
- a generally known binder may be used for the positive electrode.
- Representative examples thereof include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymers, polyvinylpyrrolidone, polyurethane, Polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, or the like may be used, but is not limited thereto.
- the negative electrode and the positive electrode may be prepared by mixing an active material and a binder, in some cases, a conductive material, a filler, and the like in a solvent to prepare a slurry-like electrode mixture, and applying the electrode mixture to each electrode current collector. Since such an electrode manufacturing method is widely known in the art, a detailed description thereof will be omitted herein.
- any one commonly used in lithium batteries may be used as it separates the negative electrode and the positive electrode and provides a passage for lithium ions to move. That is, a low-resistance to ion movement of the electrolyte and excellent electrolyte moisture content may be used.
- it may be selected from glass fiber, polyester, Teflon, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), or a combination thereof, and may be in the form of a nonwoven fabric or a woven fabric.
- a polyolefin-based polymer separator such as polyethylene or polypropylene is mainly used for lithium ion batteries, and a coated separator containing a ceramic component or a polymer material may be used to secure heat resistance or mechanical strength, and optionally single-layer or multi-layer structure can be used.
- a gel polymer electrolyte may be coated on the separator to increase battery stability.
- Representative examples of such a gel polymer include polyethylene oxide, polyvinylidene fluoride, polyacrylonitrile, and the like.
- the solid electrolyte may also serve as a separator.
- the non-aqueous electrolyte may be a liquid electrolyte including 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.
- non-aqueous electrolyte a non-aqueous electrolyte, an organic solid electrolyte, an inorganic solid electrolyte, and the like are used.
- non-aqueous electrolyte examples include N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate , gamma-butylolactone, 1,2-dimethoxy ethane, 1,2-diethoxy ethane, tetrahydroxy franc, 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, 4-methyl-1,3-dioxene, diethyl ether, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid triester, trimethoxymethane, dioxolane Aprotic organic solvents such as derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propy
- organic solid electrolyte examples include polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphoric acid ester polymers, poly agitation lysine, polyester sulfide, polyvinyl alcohol, polyvinylidene fluoride, ions
- a polymer containing a sexually dissociating group or the like can be used.
- Examples of the inorganic solid electrolyte include Li 3 N, LiI, Li 5 NI 2 , Li 3 N-LiI-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3 , Li 4 SiO 4 , Nitrides, halides, sulfates, etc. of Li such as Li 4 SiO 4 -LiI-LiOH, Li 3 PO 4 -Li 2 S-SiS 2 and the like may be used.
- the lithium salt is a material readily soluble in the non-aqueous electrolyte, for example, LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li, CF 3 SO 3 Li, LiSCN, LiC(CF 3 SO 2 ) 3 , (CF 3 SO 2 ) 2 NLi, chloroborane lithium, lower aliphatic lithium carboxylate, 4 phenyl lithium borate, and the like can be used.
- pyridine triethylphosphite, triethanolamine, cyclic ether, ethylenediamine, n-glyme, hexaphosphate triamide, nitro Benzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N,N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium salts, pyrrole, 2-methoxyethanol, aluminum trichloride, etc.
- pyridine triethylphosphite, triethanolamine
- cyclic ether ethylenediamine
- n-glyme hexaphosphate triamide
- nitro Benzene derivatives sulfur, quinone imine dyes, N-substituted oxazolidinones, N,N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium salts, pyrrole
- a halogen-containing solvent such as carbon tetrachloride and ethylene trifluoride may be further included, and carbon dioxide gas may be further included to improve high temperature storage characteristics, and FEC (fluoro-ethylene) carbonate), propene sultone (PRS), and fluoro-propylene carbonate (FPC) can be further included.
- FEC fluoro-ethylene carbonate
- PRS propene sultone
- FPC fluoro-propylene carbonate
- the lithium secondary battery according to the present invention may be used not only in a battery cell used as a power source for a small device, but also as a unit battery in a medium/large battery module including a plurality of battery cells.
- Polymerization was carried out in two steps to prepare binder particles having a core-shell structure.
- Step 1 Preparation of isoprene-based core particles
- the polymerization reaction was performed at 75° C. for about 5 hours to obtain a core composition including isoprene-based core particles and water.
- (d) butadiene (59 parts by weight), (e) styrene (33 parts by weight), (f) acrylic acid and itaconic acid (8 parts by weight), sodium polyoxyethylene lauryl ether sulfate (0.6 parts by weight) as an emulsifier ) and potassium persulfate (1.2 parts by weight) as a polymerization initiator were added to water as a solvent to prepare a second monomer mixture.
- An amount of the second monomer mixture was taken so that the weight ratio of the first monomer mixture to the second monomer mixture was 9:1, and it was added to the first binder composition.
- binder composition including binder (latex) particles including isoprene-based core particles and butadiene-based shells, and water.
- a copper foil having a thickness of 10 ⁇ m was prepared and this was used as a negative electrode current collector.
- the negative electrode mixture composition of Example 1 was applied to both sides in a loading amount of 8.0 mg/cm 2 per side of the negative electrode current collector, and an oven at 80 ° C. ) in hot air drying for 10 minutes, and then roll-pressed to a total thickness of 190 ⁇ m.
- the negative electrode of Example 1 was obtained.
- Example 1 An aluminum foil having a thickness of 20 ⁇ m was prepared and this was used as a positive electrode current collector. Using a comma coater, the positive electrode mixture composition of Example 1 was applied on both sides at a loading amount of 15.6 mg/cm 2 per one side of the negative electrode current collector, and an oven at 80 ° C. ) in hot air drying for 10 minutes, and then roll-pressed to a total thickness of 190 ⁇ m. Thus, the positive electrode of Example 1 was obtained.
- EC ethylene carbonate
- PC propylene carbonate
- DEC diethyl carbonate
- FEC fluoroethylene carbonate
- a binder composition for a negative electrode, negative electrode mixture composition, negative electrode, and secondary battery of Example 2 were prepared in the same manner as in Example 1, except that the weight ratio of the first monomer mixture and the second monomer mixture was changed.
- Example 2 the mixing of the first monomer mixture and the mixing of the second monomer mixture were the same, but the weight ratio of the first monomer mixture to the second monomer mixture was changed to 6:1.
- a binder composition for a negative electrode of Example 3 a negative electrode mixture composition, a negative electrode, and a secondary battery were prepared in the same manner as in Example 1, except that the weight ratio of the first monomer mixture and the second monomer mixture was changed.
- Example 3 the mixing of the first monomer mixture and the mixing of the second monomer mixture were the same, but the weight ratio of the first monomer mixture to the second monomer mixture was changed to 4.5:1.
- a binder composition for a negative electrode of Example 4 a negative electrode mixture composition, a negative electrode, and a secondary battery were prepared in the same manner as in Example 1, except that the mixing ratio of the first monomer mixture was changed.
- Example 4 the mixing of the second monomer mixture and the weight ratio of the first monomer mixture: the second monomer mixture were the same, but when the first monomer mixture was prepared (a) isoprene (150 parts by weight), ( b) styrene (200 parts by weight), (c) acrylic acid and itaconic acid (26 parts by weight) were used.
- a binder composition for a negative electrode of Example 5 was prepared in the same manner as in Example 1, except that the mixing ratio of the first monomer mixture was changed.
- Example 5 the mixing of the second monomer mixture and the weight ratio of the first monomer mixture to the second monomer mixture were the same, but when preparing the first monomer mixture, (a) isoprene (250 parts by weight), ( b) styrene (200 parts by weight), (c) acrylic acid and itaconic acid (26 parts by weight) were used.
- a binder composition for a negative electrode of Example 6 a negative electrode mixture composition, a negative electrode, and a secondary battery were prepared in the same manner as in Example 1, except that the mixing ratio of the second monomer mixture was changed.
- Example 6 the mixing of the first monomer mixture and the weight ratio of the first monomer mixture to the second monomer mixture were the same, but when preparing the second monomer mixture (d) butadiene (40 parts by weight), (e) styrene (52 parts by weight), (f) acrylic acid and itaconic acid (8 parts by weight) were used.
- a binder composition for a negative electrode of Example 7 a negative electrode mixture composition, a negative electrode, and a secondary battery were prepared in the same manner as in Example 1, except that the mixing ratio of the second monomer mixture was changed.
- Example 7 the mixing of the first monomer mixture and the weight ratio of the first monomer mixture: the second monomer mixture were the same, but when preparing the second monomer mixture (d) butadiene (72 parts by weight), ( e) styrene (20 parts by weight), (f) acrylic acid and itaconic acid (8 parts by weight) were used.
- Example 1 By performing only the first step of Example 1, a composition including isoprene-based latex particles and water was prepared, and this was used as a binder composition for a negative electrode of Comparative Example 1.
- a negative electrode mixture composition of Comparative Example 1, a negative electrode, and a secondary battery were prepared in the same manner as in Example 1, except that the binder composition for the negative electrode was changed.
- Example 2 The first step of Example 1 was omitted and only the second step was performed to prepare a composition including butadiene-based latex particles and water, and this was used as a binder composition for a negative electrode of Comparative Example 2.
- a negative electrode mixture composition of Comparative Example 2, a negative electrode, and a secondary battery were prepared in the same manner as in Example 1, except that the binder composition for the negative electrode was changed.
- Example 3 Using the second monomer mixture of Example 1 when preparing the core particles, and using the first monomer mixture of Example 1 when forming the shell, including latex particles including butadiene-based core particles and isoprene-based shells and water A composition was prepared, and it was used as a binder composition for a negative electrode of Comparative Example 3.
- a negative electrode mixture composition of Comparative Example 3, a negative electrode, and a secondary battery were prepared in the same manner as in Example 1, except that the binder composition for the negative electrode was changed.
- a negative electrode mixture composition of Comparative Example 4, a negative electrode, and a secondary battery were prepared in the same manner as in Example 1, except that the binder composition for the negative electrode was changed.
- Example 4 Using the first monomer mixture of Example 1 when preparing the core particles, and also using the first monomer mixture of Example 1 when forming the shell, including latex particles including the isoprene-based core particles and the isoprene-based shell, and water A composition was prepared, and it was used as a binder composition for a negative electrode of Comparative Example 4.
- a negative electrode mixture composition of Comparative Example 4, a negative electrode, and a secondary battery were prepared in the same manner as in Example 1, except that the binder composition for the negative electrode was changed.
- Each of the binders may have the form of latex particles prepared through emulsion polymerization.
- the latex particles using a particle size analyzer (NICOMP AW380, manufactured by PSS), the arithmetic average particle diameter of the binder particles in the binder composition, specifically, the average particle diameter of scattering intensity (Intensity distribution) was obtained.
- Example 1 Average particle size (nm) Viscosity (cP) Example 1 187 21 Example 2 211 21 Example 3 278 21 Example 4 178 20 Example 5 224 21 Example 6 182 20 Example 7 175 20 Comparative Example 1 105 20 Comparative Example 2 82 20 Comparative Example 3 180 21 Comparative Example 4 161 20 Comparative Example 5 256 21
- the degree of swelling of the binder with respect to the electrolyte was measured. After applying the binder dispersed in the solvent to a predetermined thickness on the PET film and drying it at 80° C. for 24 hours or more, the binder film was cut into 1.5 cm * 8 cm to prepare a specimen. The prepared specimen was supported in the electrolyte for 24 hours, and the weight before and after the electrolyte loading was measured, respectively, and the binder weight change rate was evaluated according to the following [Equation 1].
- electrolyte an electrolyte having the same composition as that used for manufacturing each lithium ion battery was used.
- Electrolyte Uptake (%) 100 ⁇ [Weight after electrolyte loading] /[Weight before electrolyte loading]
- Comparative Example 5 in which latex particles including isoprene-based core particles and isoprene-based shells were used as binders, results similar to those of Comparative Example 1 in which isoprene-based particles were used as binders were obtained.
- Comparative Example 4 in which latex particles including butadiene-based core particles and butadiene-based shells were used as binders, results similar to those of Comparative Example 2 in which butadiene-based latex particles were used as binders were obtained.
- Comparative Example 3 using latex particles including butadiene-based core particles and isoprene-based shells as a binder, the initial adhesion of the negative electrode was partially improved compared to Comparative Example 1, and the weight change before and after loading the electrolyte was partially improved compared to Comparative Example 2 stayed at the level
- the formulation of the core (first monomer mixture), the shell (the second monomer mixture), and the core:shell (first monomer mixture: second By controlling the weight ratio of the monomer mixture), it will be possible to adjust the initial adhesion and impregnation rate of the negative electrode, and furthermore, the lifespan of the secondary battery to a desired range.
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Abstract
Description
코어 | 쉘 | 코어:쉘 중량비 | |||||
이소프렌 (중량부) | 스티렌 (중량부) |
아크릴산과 이타콘산 (중량부) |
부타디엔 (중량부) |
스티렌 (중량부) |
아크릴산과 이타콘산 (중량부) |
||
실시예1 | 200 | 150 | 26 | 59 | 33 | 8 | 9:1 |
실시예2 | 200 | 150 | 26 | 88.5 | 49.5 | 12 | 6:1 |
실시예3 | 200 | 150 | 26 | 118 | 66 | 16 | 4.5:1 |
실시예4 | 150 | 200 | 26 | 59 | 33 | 8 | 9 |
실시예5 | 250 | 200 | 26 | 59 | 33 | 8 | 9 |
실시예6 | 200 | 150 | 26 | 40 | 52 | 8 | 9 |
실시예7 | 200 | 150 | 26 | 72 | 20 | 8 | 9 |
비교예1 | 200 | 150 | 26 | - | - | - | - |
비교예2 | - | - | - | 59 | 33 | 8 | - |
부타디엔 (중량부) |
스티렌 (중량부) |
아크릴산과 이타콘산 (중량부) |
이소프렌 (중량부) | 스티렌 (중량부) |
아크릴산과 이타콘산 (중량부) |
||
비교예3 | 59 | 33 | 8 | 200 | 150 | 26 | 9:1 |
부타디엔 (중량부) |
스티렌 (중량부) |
아크릴산과 이타콘산 (중량부) |
부타디엔 (중량부) |
스티렌 (중량부) |
아크릴산과 이타콘산 (중량부) |
||
비교예4 | 59 | 33 | 8 | 59 | 33 | 8 | 9:1 |
이소프렌 (중량부) | 스티렌(중량부) | 아크릴산과 이타콘산 (중량부) |
이소프렌 (중량부) | 스티렌 (중량부) |
아크릴산과 이타콘산 (중량부) |
||
비교예5 | 200 | 150 | 26 | 200 | 150 | 26 | 9:1 |
평균 입경 (nm) | 점도 (cP) | |
실시예1 | 187 | 21 |
실시예2 | 211 | 21 |
실시예3 | 278 | 21 |
실시예4 | 178 | 20 |
실시예5 | 224 | 21 |
실시예6 | 182 | 20 |
실시예7 | 175 | 20 |
비교예1 | 105 | 20 |
비교예2 | 82 | 20 |
비교예3 | 180 | 21 |
비교예4 | 161 | 20 |
비교예5 | 256 | 21 |
음극 접착력 (gf/cm) |
전해액 Uptake (%) | 300 사이클 후 이차 전지의 용량 유지율 (%) | |
실시예 1 | 20.8 | 90 | 92 |
실시예 2 | 22.5 | 105 | 88 |
실시예 3 | 23.5 | 114 | 88 |
실시예 4 | 20.8 | 101 | 89 |
실시예 5 | 20.7 | 82 | 93 |
실시예 6 | 18.5 | 90 | 92 |
실시예 7 | 21.9 | 91 | 91 |
비교예 1 | 12.2 | 92 | 87 |
비교예 2 | 21.0 | 125 | 86 |
비교예 3 | 16.4 | 120 | 86 |
비교예 4 | 22 | 123 | 86 |
비교예 5 | 12.5 | 90 | 92 |
Claims (20)
- 코어-쉘 구조의 바인더 입자를 포함하고,상기 코어-쉘 구조의 바인더 입자는, 이소프렌계 단량체 유래 반복 단위를 포함하는 공중합체 코어 입자; 및 상기 코어 입자의 표면에 위치하고, 부타디엔계 단량체 유래 반복 단위를 포함하는 공중합체 쉘;을 포함하는,이차 전지의 음극용 바인더.
- 제1항에 있어서상기 코어 입자는,(a) 이소프렌계 제1 단량체 유래 제1 반복 단위,(b) 방향족 비닐계 제2 단량체 유래 제2 반복 단위 및(c) 불포화 카르본산계 제3 단량체 유래 제3 반복 단위를 포함하는 공중합체인,이차 전지의 음극용 바인더.
- 제2항에 있어서,상기 코어 입자의 총량 (100 중량%) 중,(a) 이소프렌계 제1 단량체 유래 제1 반복 단위 30 내지 65 중량%,(b) 방향족 비닐계 제2 단량체 유래 제2 반복 단위 30 내지 65 중량% 및(c) 불포화 카르본산계 제3 단량체 유래 제3 반복 단위 0.1 내지 10 중량%가 포함되는,이차 전지의 음극용 바인더.
- 제2항에 있어서,상기 제2 단량체는,스티렌, α-메틸스티렌, β-메틸스티렌, p-t-부틸스티렌, 클로로스티렌, 비닐벤조산, 비닐벤조산메틸, 비닐나프탈렌, 클로로메틸스티렌, 히드록시메틸스티렌 및 디비닐벤젠으로 이루어진 군으로부터 선택된 1종 이상인,이차 전지의 음극용 바인더.
- 제2항에 있어서,상기 제3 단량체는,아크릴산, 메타크릴산, 말레인산, 푸마르산, 글루타르산, 이타콘산, 테트라하이드로프탈산, 크로톤산, 이소크로톤산, 및 나딕산으로 이루어진 군에서 선택된 1종 이상인,이차 전지의 음극용 바인더.
- 제1항에 있어서상기 쉘은,(d) 부타디엔계 제4 단량체 유래 제4 반복 단위,(e) 방향족 비닐계 제5 단량체 유래 제5 반복 단위 및(f) 불포화 카르본산계 제6 단량체 유래 제6 반복 단위를 포함하는 공중합체인,이차 전지의 음극용 바인더.
- 제6항에 있어서,상기 쉘의 총량 (100 중량%) 중,(d) 부타디엔계 제4 단량체 유래 제4 반복 단위 30 내지 85 중량%,(e) 방향족 비닐계 제5 단량체 유래 제5 반복 단위 10 내지 65 중량% 및(f) 불포화 카르본산계 제6 단량체 유래 제6 반복 단위 0.1 내지 15 중량%가 포함되는,이차 전지의 음극용 바인더.
- 제6항에 있어서,상기 제5 단량체는,스티렌, α-메틸스티렌, β-메틸스티렌, p-t-부틸스티렌, 클로로스티렌, 비닐벤조산, 비닐벤조산메틸, 비닐나프탈렌, 클로로메틸스티렌, 히드록시메틸스티렌 및 디비닐벤젠으로 이루어진 군으로부터 선택된 1종 이상인,이차 전지의 음극용 바인더.
- 제6항에 있어서,상기 제6 단량체는,아크릴산, 메타크릴산, 말레인산, 푸마르산, 글루타르산, 이타콘산, 테트라하이드로프탈산, 크로톤산, 이소크로톤산, 및 나딕산으로 이루어진 군에서 선택된 1종 이상인,이차 전지의 음극용 바인더.
- 제1항에 있어서,상기 코어 입자 및 상기 쉘의 중량비(코어:쉘)는,1:1 내지 15:1인,이차 전지의 음극용 바인더.
- 제1항에 있어서,상기 코어-쉘 구조의 바인더 입자는,90 내지 500 nm의 평균 입경을 갖는 라텍스 입자인,이차 전지의 음극용 바인더.
- 제1항에 있어서,수성 용매를 더 포함하는,이차 전지의 음극용 바인더.
- 제12항에 있어서,상기 수성 용매는,상기 코어-쉘 구조의 바인더 입자 100 중량부에 대하여, 50 내지 1,000 중량부로 포함되는,이차 전지의 음극용 바인더.
- 이소프렌계 단량체를 포함하는 제1 단량체 혼합물을 중합시켜, 이소프렌계 단량체 유래 반복 단위를 포함하는 공중합체 코어 입자를 제조하는 단계; 및부타디엔계 단량체를 포함하는 제2 단량체 혼합물을 상기 코어 입자의 존재 하에 중합시켜, 부타디엔계 단량체 유래 반복 단위를 포함하는 공중합체 쉘을 상기 코어 입자의 표면에 형성하는 단계;를 포함하는,이차 전지의 음극용 바인더의 제조 방법.
- 제14항에 있어서,상기 제1 단량체 혼합물은,(a) 이소프렌계 제1 단량체, (b) 방향족 비닐계 제2 단량체 및 (c) 불포화 카르본산계 제3 단량체를 포함하는,이차 전지의 음극용 바인더의 제조 방법.
- 제14항에 있어서,상기 제2 단량체 혼합물은,(d) 부타디엔계 제4 단량체, (e) 방향족 비닐계 제5 단량체 및 (f) 불포화 카르본산계 제6 단량체를 포함하는,이차 전지의 음극용 바인더의 제조 방법.
- 제14항에 있어서,상기 제1 단량체 혼합물의 중합 및 상기 제2 단량체 혼합물의 중합은, 각각 독립적으로,수성 용매, 유화제 및 중합 개시제의 존재 하에 수행되는,이차 전지의 음극용 바인더의 제조 방법.
- 제1항의 이차 전지 음극용 바인더; 및음극 활물질;을 포함하는,이차 전지의 음극 합제.
- 제18항의 음극 합제를 포함하는 음극 합제 층; 및음극 집전체;를 포함하는,이차 전지의 음극.
- 제19항의 음극;양극; 및전해질;을 포함하는,이차 전지.
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WO2019172281A1 (ja) * | 2018-03-07 | 2019-09-12 | 日本ゼオン株式会社 | 非水系二次電池電極用バインダー組成物およびその製造方法、非水系二次電池電極用スラリー組成物、非水系二次電池用電極、並びに、非水系二次電池 |
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2021
- 2021-10-20 JP JP2023522526A patent/JP2023545305A/ja active Pending
- 2021-10-20 WO PCT/KR2021/014716 patent/WO2022086173A1/ko active Application Filing
- 2021-10-20 EP EP21883241.8A patent/EP4210134A1/en active Pending
- 2021-10-20 US US18/032,698 patent/US20230387415A1/en active Pending
- 2021-10-20 CN CN202180068679.6A patent/CN116323763A/zh active Pending
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KR101698745B1 (ko) * | 2015-08-03 | 2017-01-23 | 주식회사 한솔케미칼 | 리튬 이온 이차전지 음극용 코어-쉘 구조의 바인더 및 이의 제조방법, 및 상기 바인더를 포함하는 슬러리 |
KR101683723B1 (ko) * | 2016-03-24 | 2016-12-09 | (주)상아프론테크 | 2차 전지 음극용 코팅제, 이를 이용한 2차 전지용 음극 및 이의 제조방법 |
WO2019172281A1 (ja) * | 2018-03-07 | 2019-09-12 | 日本ゼオン株式会社 | 非水系二次電池電極用バインダー組成物およびその製造方法、非水系二次電池電極用スラリー組成物、非水系二次電池用電極、並びに、非水系二次電池 |
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US20230387415A1 (en) | 2023-11-30 |
CN116323763A (zh) | 2023-06-23 |
EP4210134A1 (en) | 2023-07-12 |
KR20220054055A (ko) | 2022-05-02 |
JP2023545305A (ja) | 2023-10-27 |
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