WO2021253675A1 - Composition de liant pour batterie secondaire - Google Patents

Composition de liant pour batterie secondaire Download PDF

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Publication number
WO2021253675A1
WO2021253675A1 PCT/CN2020/117789 CN2020117789W WO2021253675A1 WO 2021253675 A1 WO2021253675 A1 WO 2021253675A1 CN 2020117789 W CN2020117789 W CN 2020117789W WO 2021253675 A1 WO2021253675 A1 WO 2021253675A1
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WIPO (PCT)
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binder composition
acid
rpm
containing monomer
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PCT/CN2020/117789
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English (en)
Inventor
Kam Piu Ho
Yingkai JIANG
Tao Gong
Original Assignee
Guangdong Haozhi Technology Co. Limited
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Priority claimed from PCT/CN2020/096672 external-priority patent/WO2021253302A1/fr
Application filed by Guangdong Haozhi Technology Co. Limited filed Critical Guangdong Haozhi Technology Co. Limited
Priority to KR1020227046323A priority Critical patent/KR20230028734A/ko
Priority to US17/910,813 priority patent/US20230121093A1/en
Priority to CA3183233A priority patent/CA3183233A1/fr
Priority to CN202080062552.9A priority patent/CN114342125B/zh
Priority to EP20940735.2A priority patent/EP4104221A1/fr
Priority to CN202410295012.5A priority patent/CN118016892A/zh
Priority to JP2022562146A priority patent/JP2023529531A/ja
Priority to AU2020453243A priority patent/AU2020453243A1/en
Priority to AU2020453945A priority patent/AU2020453945A1/en
Priority to KR1020227043316A priority patent/KR20230025778A/ko
Priority to CN202080067229.0A priority patent/CN114503336B/zh
Priority to PCT/CN2020/139555 priority patent/WO2021253787A1/fr
Priority to CA3183236A priority patent/CA3183236A1/fr
Priority to JP2022568795A priority patent/JP7516557B2/ja
Priority to EP20941173.5A priority patent/EP4169108A4/fr
Priority to US17/912,038 priority patent/US20230138359A1/en
Priority to PCT/CN2020/141488 priority patent/WO2021253796A1/fr
Priority to KR1020237001858A priority patent/KR102712570B1/ko
Priority to CA3183237A priority patent/CA3183237A1/fr
Priority to EP21825136.1A priority patent/EP4169095A4/fr
Priority to AU2021291911A priority patent/AU2021291911A1/en
Priority to CN202180007279.4A priority patent/CN114846654B/zh
Priority to US17/914,367 priority patent/US20230105056A1/en
Priority to PCT/CN2021/076466 priority patent/WO2021253849A1/fr
Priority to JP2022578586A priority patent/JP2023530012A/ja
Priority to CN202180005210.8A priority patent/CN114424365B/zh
Priority to KR1020227034091A priority patent/KR102719375B1/ko
Priority to CN202410220707.7A priority patent/CN118099430A/zh
Priority to US17/797,116 priority patent/US20230073006A1/en
Priority to CA3183234A priority patent/CA3183234A1/fr
Priority to EP21771882.4A priority patent/EP4088331A1/fr
Priority to PCT/CN2021/080568 priority patent/WO2021185183A1/fr
Priority to JP2022555710A priority patent/JP2023517376A/ja
Priority to US17/922,380 priority patent/US20230175095A1/en
Priority to EP21827044.5A priority patent/EP4169110A4/fr
Priority to PCT/CN2021/080684 priority patent/WO2021253887A1/fr
Priority to PCT/CN2021/080683 priority patent/WO2021253886A1/fr
Priority to US17/916,590 priority patent/US20230340379A1/en
Priority to PCT/CN2021/080682 priority patent/WO2021253885A1/fr
Priority to PCT/CN2021/080670 priority patent/WO2021253883A1/fr
Priority to CN202180011083.2A priority patent/CN115023843A/zh
Priority to US17/923,925 priority patent/US20230178820A1/en
Priority to PCT/CN2021/080685 priority patent/WO2021253888A1/fr
Priority to JP2022577450A priority patent/JP2023530345A/ja
Priority to US17/923,239 priority patent/US20230182462A1/en
Priority to CN202180011327.7A priority patent/CN115023844A/zh
Priority to PCT/CN2021/080681 priority patent/WO2021253884A1/fr
Priority to KR1020227046218A priority patent/KR20230025806A/ko
Priority to US17/917,949 priority patent/US20230136670A1/en
Priority to CN202180024380.0A priority patent/CN115336085A/zh
Priority to JP2022572495A priority patent/JP2023529583A/ja
Priority to KR1020227046182A priority patent/KR20230025412A/ko
Priority to CN202180012653.XA priority patent/CN115053380A/zh
Priority to CN202180013075.1A priority patent/CN115053381A/zh
Priority to EP21825583.4A priority patent/EP4118704A4/fr
Priority to TW110110085A priority patent/TW202143536A/zh
Priority to AU2021290598A priority patent/AU2021290598A1/en
Priority to JP2022571743A priority patent/JP2023530075A/ja
Priority to PCT/CN2021/097669 priority patent/WO2021254138A1/fr
Priority to US17/915,493 priority patent/US20230198039A1/en
Priority to KR1020227046178A priority patent/KR20230025805A/ko
Priority to EP21826097.4A priority patent/EP4169106A4/fr
Priority to CA3183238A priority patent/CA3183238A1/fr
Priority to CN202180007275.6A priority patent/CN114868298A/zh
Priority to US17/912,851 priority patent/US20230142072A1/en
Priority to PCT/CN2021/098036 priority patent/WO2021254157A1/fr
Priority to CN202180006980.4A priority patent/CN114762152B/zh
Priority to CN202180006979.1A priority patent/CN114762145A/zh
Priority to PCT/CN2021/098037 priority patent/WO2021254158A1/fr
Priority to US17/925,607 priority patent/US20230207813A1/en
Priority to KR1020237001934A priority patent/KR20230025707A/ko
Priority to CN202180032081.1A priority patent/CN115668547A/zh
Priority to KR1020237002041A priority patent/KR20230027206A/ko
Priority to US17/925,836 priority patent/US20230187639A1/en
Priority to PCT/CN2021/098918 priority patent/WO2021254215A1/fr
Priority to JP2022577317A priority patent/JP2023529987A/ja
Priority to JP2022575181A priority patent/JP2023529661A/ja
Priority to PCT/CN2021/098950 priority patent/WO2021254218A1/fr
Priority to EP21827079.1A priority patent/EP4169098A1/fr
Priority to CN202180032063.3A priority patent/CN115568289A/zh
Priority to EP21826609.6A priority patent/EP4143905A1/fr
Priority to US17/926,995 priority patent/US20230223517A1/en
Priority to JP2022576796A priority patent/JP2023530929A/ja
Priority to CN202180024379.8A priority patent/CN115380096A/zh
Priority to EP21824876.3A priority patent/EP4136182A1/fr
Priority to CA3183239A priority patent/CA3183239A1/fr
Priority to AU2021292254A priority patent/AU2021292254A1/en
Priority to KR1020227046166A priority patent/KR20230024297A/ko
Priority to PCT/CN2021/099368 priority patent/WO2021254245A1/fr
Priority to US17/924,375 priority patent/US20230178740A1/en
Priority to TW110121751A priority patent/TW202211529A/zh
Priority to AU2021291990A priority patent/AU2021291990A1/en
Priority to TW110121754A priority patent/TW202200641A/zh
Priority to TW110121755A priority patent/TW202200393A/zh
Priority to JP2022577379A priority patent/JP2023530330A/ja
Priority to KR1020237001859A priority patent/KR20230027194A/ko
Priority to PCT/CN2021/099950 priority patent/WO2021254300A1/fr
Priority to TW110121758A priority patent/TW202201830A/zh
Priority to TW110121756A priority patent/TW202200394A/zh
Priority to CN202180036152.5A priority patent/CN115668549A/zh
Priority to TW110121757A priority patent/TW202200395A/zh
Priority to CA3183240A priority patent/CA3183240A1/fr
Priority to US17/927,750 priority patent/US20230216055A1/en
Priority to EP21827012.2A priority patent/EP4169097A4/fr
Priority to TW110121967A priority patent/TW202200396A/zh
Priority to PCT/CN2021/100365 priority patent/WO2021254393A1/fr
Priority to TW110121972A priority patent/TW202201835A/zh
Priority to TW110121973A priority patent/TW202207506A/zh
Priority to US18/007,753 priority patent/US20230299372A1/en
Priority to AU2021290702A priority patent/AU2021290702A1/en
Priority to EP21826301.0A priority patent/EP4169109A4/fr
Priority to TW110121966A priority patent/TW202211523A/zh
Priority to TW110121974A priority patent/TW202211525A/zh
Priority to CA3183241A priority patent/CA3183241A1/fr
Priority to TW110121971A priority patent/TW202211524A/zh
Priority to CN202180041284.7A priority patent/CN115885408A/zh
Priority to TW110121968A priority patent/TW202200397A/zh
Priority to JP2022577316A priority patent/JP2023529986A/ja
Priority to KR1020237002049A priority patent/KR20230027207A/ko
Priority to TW110121969A priority patent/TW202200398A/zh
Priority to TW110121970A priority patent/TW202210530A/zh
Priority to TW110122185A priority patent/TW202220271A/zh
Publication of WO2021253675A1 publication Critical patent/WO2021253675A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/18—Homopolymers or copolymers of nitriles
    • C09J133/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • 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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 the field of batteries.
  • this invention relates to a binder composition for lithium-ion batteries.
  • LIBs lithium-ion batteries
  • EV electric vehicles
  • grid energy storage high-performance, low-cost LIBs are currently offering one of the most promising options for large-scale energy storage devices.
  • lithium-ion battery electrodes are manufactured by casting an organic-based slurry onto a metallic current collector.
  • the slurry contains electrode active material, conductive carbon, and binder in an organic solvent.
  • the binder provides a good electrochemical stability, holds together the electrode active materials and adheres them to the current collector in the fabrication of electrodes.
  • Polyvinylidene fluoride (PVDF) is one of the most commonly used binders in the commercial lithium-ion battery industry. However, PVDF is insoluble in water and can only dissolve in some specific organic solvents such as N-methyl-2-pyrrolidone (NMP) which is flammable and toxic and hence requires specific handling.
  • NMP N-methyl-2-pyrrolidone
  • NMP recovery system must be in place during the drying process to recover NMP vapors. This will generate significant costs in the manufacturing process since it requires a large capital investment.
  • solvents such as aqueous solvents, most commonly water, is preferred in the present invention since it can reduce the large capital cost of the recovery system.
  • aqueous binders such as carboxymethyl cellulose (CMC) and styrene-butadiene rubber (SBR) exhibit only marginal adhesion capability and poor cycle life.
  • SBR in particular, requires a thickening agent in regulating the binder viscosity. Further, SBR exhibits high expandability and undesirable agglomeration characteristics resulting in inhomogeneous dispersion, high electrode resistance and poor performance.
  • cathodes are at high voltage. Most rubbers including SBR are only stable at the low voltage of the anode and will decompose at high voltage. Therefore, their applications, especially in cathodes, are somewhat limited.
  • EP Patent Application Publication No. 2555293 B1 discloses a water-based electrode slurry for a lithium ion-containing electrochemical cell.
  • the slurry comprises a combination of PVDF and SBR and at least one of polyacrylic acid (PAA) and CMC in an aqueous solution and an electrochemically active material.
  • PAA polyacrylic acid
  • the proposed invention attempts to combine PVDF with a water-based slurry which allows easier handling and less environmental pollution and reduced costs while keeping the known chemical and electrochemical advantages of PVDF as a binder i.e. electrochemical stability, lifetime stability, reduced binder content enables higher C-rates, etc.
  • the slurry consists of fluorine-containing binder material nonetheless.
  • PVDF is highly fluorinated and toxic when exposed to thermal decomposition, which pose risks to the health of people and the environment.
  • a binder composition for a secondary battery electrode comprising a copolymer and a dispersion medium, wherein the copolymer comprises a structural unit (a) derived from a carboxylic acid group-containing monomer, a structural unit (b) derived from an amide group-containing monomer and a structural unit (c) derived from a nitrile group-containing monomer, with an improved binding capability.
  • battery cells comprising the cathode prepared using the binder composition disclosed herein exhibits exceptional electrochemical performance.
  • Figure 1 is a flow chart of an embodiment illustrating the steps for preparing a binder composition.
  • a binder composition for a secondary battery electrode comprising a copolymer and a dispersion medium, wherein the copolymer comprises a structural unit (a) derived from a carboxylic acid group-containing monomer, a structural unit (b) derived from an amide group-containing monomer and a structural unit (c) derived from a nitrile group-containing monomer.
  • Electrode refers to a “cathode” or an “anode. ”
  • positive electrode is used interchangeably with cathode.
  • negative electrode is used interchangeably with anode.
  • binder refers to a chemical compound, mixture of compounds, or polymer which form colloidal solutions or colloidal dispersions in a dispersion medium such as water, and is used to hold an electrode material and/or a conductive agent in place and adhere them onto a conductive metal part to form an electrode.
  • the electrode does not comprise any conductive agent.
  • conductive agent refers to a material which is chemically inactive and has good electrical conductivity. Therefore, the conductive agent is often mixed with an electrode active material at the time of forming an electrode to improve electrical conductivity of the electrode.
  • polymer refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type.
  • the generic term “polymer” embraces the terms “homopolymer” as well as “copolymer” .
  • homopolymer refers to a polymer prepared by the polymerization of the same type of monomer.
  • copolymer refers to a polymer prepared by the polymerization of two or more different types of monomers.
  • unsaturated refers to a moiety having one or more units of unsaturation.
  • alkyl or “alkyl group” refers to a univalent group having the general formula C n H 2n+1 derived from removing a hydrogen atom from a saturated, unbranched or branched aliphatic hydrocarbon, where n is an integer, or an integer between 1 and 20, or between 1 and 8.
  • alkyl groups include, but are not limited to, (C 1 –C 8 ) alkyl groups, such as methyl, ethyl, propyl, isopropyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-3-butyl, 2, 2-dimethyl-1-propyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2, 2-dimethyl-1-butyl, 3, 3-dimethyl-1-butyl, 2-ethyl-1-butyl, butyl, isobutyl, t–butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl and octyl.
  • C 1 –C 8 alkyl groups such as
  • Longer alkyl groups include nonyl and decyl groups.
  • An alkyl group can be unsubstituted or substituted with one or more suitable substituents.
  • the alkyl group can be branched or unbranched. In some embodiments, the alkyl group contains at least 2, 3, 4, 5, 6, 7, or 8 carbon atoms.
  • cycloalkyl refers to a saturated or unsaturated cyclic non-aromatic hydrocarbon radical having a single ring or multiple condensed rings.
  • cycloalkyl groups include, but are not limited to, (C 3 -C 7 ) cycloalkyl groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl, and saturated cyclic and bicyclic terpenes and (C 3 -C 7 ) cycloalkenyl groups, such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and cycloheptenyl, and unsaturated cyclic and bicyclic terpenes.
  • a cycloalkyl group can be unsubstituted or substituted by one or two suitable substituents. Furthermore, the cycloalkyl group can be monocyclic or polycyclic. In some embodiments, the cycloalkyl group contains at least 5, 6, 7, 8, 9, or 10 carbon atoms.
  • alkoxy refers to an alkyl group, as previously defined, attached to the principal carbon chain through an oxygen atom.
  • Some non-limiting examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, and the like.
  • the alkoxy defined above may be substituted or unsubstituted, wherein the substituent may be, but is not limited to, deuterium, hydroxy, amino, halo, cyano, alkoxy, alkyl, alkenyl, alkynyl, mercapto, nitro, and the like.
  • alkenyl refers to an unsaturated straight chain, branched chain, or cyclic hydrocarbon radical that contains one or more carbon-carbon double bonds.
  • alkenyl groups include, but are not limited to, ethenyl, 1-propenyl, or 2-propenyl, which may optionally be substituted on one or more of the carbon atoms of the radical.
  • aryl refers to an organic radical derived from a monocyclic or polycyclic aromatic hydrocarbon by removing a hydrogen atom.
  • Non-limiting examples of the aryl group include phenyl, naphthyl, benzyl, or tolanyl group, sexiphenylene, phenanthrenyl, anthracenyl, coronenyl, and tolanylphenyl.
  • An aryl group can be unsubstituted or substituted with one or more suitable substituents.
  • the aryl group can be monocyclic or polycyclic. In some embodiments, the aryl group contains at least 6, 7, 8, 9, or 10 carbon atoms.
  • aliphatic refers to a C 1 to C 30 alkyl group, a C 2 to C 30 alkenyl group, a C 2 to C 30 alkynyl group, a C 1 to C 30 alkylene group, a C 2 to C 30 alkenylene group, or a C 2 to C 30 alkynylene group.
  • the alkyl group contains at least 2, 3, 4, 5, 6, 7, or 8 carbon atoms.
  • aromatic refers to groups comprising aromatic hydrocarbon rings, optionally including heteroatoms or substituents.
  • groups include, but are not limited to, phenyl, tolyl, biphenyl, o-terphenyl, m-terphenyl, p-terphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, triphenylenyl, and derivatives thereof.
  • substituted refers to that at least one hydrogen atom of that compound or chemical moiety is replaced with a second chemical moiety.
  • substituents include, but are not limited to, halogen; alkyl; heteroalkyl; alkenyl; alkynyl; aryl, heteroaryl, hydroxyl; alkoxyl; amino; nitro; thiol; thioether; imine; cyano; amido; phosphonato; phosphine; carboxyl; thiocarbonyl; sulfonyl; sulfonamide; acyl; formyl; acyloxy; alkoxycarbonyl; oxo; haloalkyl (e.g., trifluoromethyl) ; carbocyclic cycloalkyl, which can be monocyclic or fused or non-fused polycyclic (e.g., cyclopropyl, cyclobuty
  • halogen or “halo” refers to F, Cl, Br or I.
  • monomeric unit refers to the constitutional unit contributed by a single monomer to the structure of a polymer.
  • structural unit refers to the total monomeric units contributed by the same monomer type in a polymer.
  • carboxylic salt group refers to the carboxylate salt formed when a carboxylic acid reacts with a base.
  • the proton of the carboxylic acid is replaced with a metal cation.
  • the proton of the carboxylic acid is replaced with an ammonium ion.
  • applying refers to an act of laying or spreading a substance on a surface.
  • the term “current collector” refers to any conductive substrate, which is in contact with an electrode layer and is capable of conducting an electrical current flowing to electrodes during discharging or charging a secondary battery.
  • the current collector include a single conductive metal layer or substrate and a single conductive metal layer or substrate with an overlying conductive coating layer, such as a carbon black-based coating layer.
  • the conductive metal layer or substrate may be in the form of a foil or a porous body having a three-dimensional network structure, and may be a polymeric or metallic material or a metalized polymer. In some embodiments, the three-dimensional porous current collector is covered with a conformal carbon layer.
  • electrode layer refers to a layer, which is in contact with a current collector, that comprises an electrochemically active material.
  • the electrode layer is made by applying a coating on to the current collector.
  • the electrode layer is located on the surface of the current collector.
  • the three-dimensional porous current collector is coated conformally with an electrode layer.
  • room temperature refers to indoor temperatures from about 18 °C to about 30 °C, e.g., 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 °C. In some embodiments, room temperature refers to a temperature of about 20 °C +/-1 °C or +/-2 °C or +/-3 °C. In other embodiments, room temperature refers to a temperature of about 22 °C or about 25 °C.
  • particle size D50 refers to a volume-based accumulative 50%size (D50) , which is a particle size at a point of 50%on an accumulative curve (i.e., a diameter of a particle in the 50th percentile (median) of the volumes of particles) when the accumulative curve is drawn so that a particle size distribution is obtained on the volume basis and the whole volume is 100%.
  • the particle size D50 means a volume-averaged particle size of secondary particles which can be formed by mutual agglomeration of primary particles, and in a case where the particles are composed of the primary particles only, it means a volume-averaged particle size of the primary particles.
  • polydispersity index refers to a ratio of the weight average molecular weight (M w ) relative to the number average molecular weight (M n ) . It is a measure of the distribution of the molecular weight within a given binder composition sample.
  • solid content refers to the amount of non-volatile material remaining after evaporation.
  • mean roughness depth or “R z ” refers to the arithmetic mean value of the single roughness depths of consecutive sampling lengths of a current collector.
  • peeling strength refers to the amount of force required to separate a current collector and an electrode active material coating that are bonded to each other. It is a measure of the binding strength between such two materials and is usually expressed in N/cm.
  • adheresive strength refers to the amount of force required to separate a current collector and a binder composition coating that are bonded to each other. It is a measure of the adhesion strength between such two materials and is usually expressed in N/cm.
  • swelling refers to a volumetric evolution of binder composition after soaking in the electrolyte or the uptake of electrolyte due to electrolyte-binder interactions.
  • C rate refers to the charging or discharging rate of a cell or battery, expressed in terms of its total storage capacity in Ah or mAh. For example, a rate of 1 C means utilization of all of the stored energy in one hour; a 0.1 C means utilization of 10%of the energy in one hour or full energy in 10 hours; and a 5 C means utilization of full energy in 12 minutes.
  • ampere-hour (Ah) refers to a unit used in specifying the storage capacity of a battery.
  • a battery with 1 Ah capacity can supply a current of one ampere for one hour or 0.5 A for two hours, etc. Therefore, 1 ampere-hour (Ah) is the equivalent of 3,600 coulombs of electrical charge.
  • miniampere-hour (mAh) also refers to a unit of the storage capacity of a battery and is 1/1,000 of an ampere-hour.
  • battery cycle life refers to the number of complete charge/discharge cycles a battery can perform before its nominal capacity falls below 80%of its initial rated capacity.
  • Capacity is a characteristic of an electrochemical cell that refers to the total amount of electrical charge an electrochemical cell, such as a battery, is able to hold. Capacity is typically expressed in units of ampere-hours.
  • specific capacity refers to the capacity output of an electrochemical cell, such as a battery, per unit weight, usually expressed in Ah/kg or mAh/g.
  • cathodes are often prepared by dispersing a cathode active material, a binder material and a conductive agent in an organic solvent such as N-methyl-2-pyrrolidone (NMP) to form a cathode slurry, then coating the cathode slurry onto a current collector and drying it.
  • NMP N-methyl-2-pyrrolidone
  • binders influence on cell performance is underestimated, as they are considered as electrochemically inactive materials.
  • the aim of a binder is to adhere the active material particles and the conductive agent together to form a continuous electrical conduction path to the current collector.
  • a binder material should be capable of facilitating electron and ion transportation to reduce the impedance between the current collector and the electrode materials and have sufficient elasticity to prevent the electrode from swelling due to volume expansion and contraction during charging and discharging.
  • PVDF Polyvinylidene fluoride
  • Carboxymethyl cellulose (CMC) and styrene butadiene rubber (SBR) are some of the typical aqueous binders that have already been used in large-scale commercial applications. However, these binders have limited binding strengths and capabilities in preventing electrode swelling. Furthermore, within the battery, cathodes are at high voltage. Most rubbers including SBR are only stable at the low voltage of the anode and will decompose at high voltage. Therefore, their applications, especially in cathodes, are somewhat limited.
  • the present invention provides a method of preparing an aqueous binder composition comprising a copolymer and a dispersion medium, wherein the copolymer comprises a structural unit (a) derived from a carboxylic acid group-containing monomer, a structural unit (b) derived from an amide group-containing monomer and a structural unit (c) derived from a nitrile group-containing monomer.
  • Figure 1 is a flow chart of an embodiment illustrating the steps of method 100 for preparing a binder composition. It is found that the binder composition described herein exhibits an enhanced adhesive capability and flexibility and simultaneously has the unexpected effect of improving the capacity and electrochemical performance of cathodes formed therefrom.
  • the binder composition described herein is produced via polymerization that involves monomers, polymers or monomer-polymer complexes being dispersed in an aqueous phase, with generation of free radicals with a water-soluble free radical initiator.
  • the neutralizing solution is prepared by dissolving the neutralizing agent in water.
  • the first suspension is formed by adding a neutralizing solution into a dispersion medium in step 101. Addition of neutralizing solution aims to improve polymerization stability and provide a pH range in which the initiator that is added at a later stage is capable of generating free radicals.
  • Neutralizing agents are commonly used for pH adjustment.
  • the neutralizing agent include alkaline aqueous solutions.
  • the neutralizing agent may be selected from the group consisting of ammonia, sodium bicarbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, magnesium hydroxide, calcium hydroxide, triethylamine, dimethylethanolamine (DMEA) , sodium carbonate, lithium carbonate, lithium bicarbonate and combinations thereof.
  • a dispersion medium is used as a solvent for the free radical initiators, neutralizing agents and other constituents.
  • the binder composition disclosed herein is prepared by an aqueous processing method in which water is used as the dispersion medium.
  • the dispersion medium can further comprise a hydrophilic solvent selected from the group consisting of ethanol, isopropanol, n-propanol, tert-butanol, n-butanol, dimethylacetamide (DMAc) , dimethylformamide (DMF) , N-methylpyrrolidone (NMP) , methyl ethyl ketone (MEK) , ethyl acetate (EA) , butyl acetate (BA) and combinations thereof.
  • a hydrophilic solvent selected from the group consisting of ethanol, isopropanol, n-propanol, tert-butanol, n-butanol, dimethylacetamide (DMAc) , dimethylformamide (DMF) , N-methylpyrrolidone (NMP) , methyl ethyl ketone (MEK) , ethyl acetate (EA) , butyl
  • the dispersion medium is free of water, ethanol, isopropanol, n-propanol, tert-butanol, n-butanol, dimethylacetamide (DMAc) , dimethylformamide (DMF) , N-methylpyrrolidone (NMP) , methyl ethyl ketone (MEK) , ethyl acetate (EA) or butyl acetate (BA) .
  • DMAc dimethylacetamide
  • DMF dimethylformamide
  • NMP N-methylpyrrolidone
  • MEK methyl ethyl ketone
  • EA ethyl acetate
  • BA butyl acetate
  • a second suspension is formed by adding a carboxylic acid group-containing monomer into the first suspension in step 102.
  • a second suspension is formed by adding a carboxylic acid group-containing monomer solution into the first suspension.
  • the carboxylic acid group-containing monomer solution can be prepared by dissolving a carboxylic acid group-containing monomer in water.
  • Structural unit (a) is derived from a carboxylic acid group-containing monomer. Any monomer that has at least one carboxylic acid group may be used as carboxylic acid group-containing monomer without any specific limitations.
  • the carboxylic acid group-containing monomer is acrylic acid, methacrylic acid, crotonic acid, 2-butyl crotonic acid, cinnamic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, tetraconic acid or a combination thereof.
  • the carboxylic acid group-containing monomer is 2-ethylacrylic acid, isocrotonic acid, cis-2-pentenoic acid, trans-2-pentenoic acid, angelic acid, tiglic acid, 3, 3-dimethyl acrylic acid, 3-propyl acrylic acid, trans-2-methyl-3-ethyl acrylic acid, cis-2-methyl-3-ethyl acrylic acid, 3-isopropyl acrylic acid, trans-3-methyl-3-ethyl acrylic acid, cis-3-methyl-3-ethyl acrylic acid, 2-isopropyl acrylic acid, trimethyl acrylic acid, 2-methyl-3, 3-diethyl acrylic acid, 3-butyl acrylic acid, 2-butyl acrylic acid, 2-pentyl acrylic acid, 2-methyl-2-hexenoic acid, trans-3-methyl-2-hexenoic acid, 3-methyl-3-propyl acrylic acid, 2-ethyl-3-propyl acrylic acid, 2, 3-diethyl acrylic acid, 3, 3-diethyl acrylic acid, 3-diethyl
  • the carboxylic acid group-containing monomer is methyl maleic acid, dimethyl maleic acid, phenyl maleic acid, bromo maleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid, difluoro maleic acid, nonyl hydrogen maleate, decyl hydrogen maleate, dodecyl hydrogen maleate, octadecyl hydrogen maleate, fluoroalkyl hydrogen maleate or a combination thereof.
  • the carboxylic acid group-containing monomer is maleic anhydride, methyl maleic anhydride, dimethyl maleic anhydride, acrylic anhydride, methacrylic anhydride, methacrolein, methacryloyl chloride, methacryloyl fluoride, methacryloyl bromide, or a combination thereof.
  • the proportion of the carboxylic acid group-containing monomer is from about 40%to about 70%, from about 40%to about 68%, from about 40%to about 66%, from about 40%to about 65%, from about 40%to about 64%, from about 40%to about 63%, from about 40%to about 62%, from about 40%to about 61%, from about 40%to about 60%, from about 40%to about 59%, from about 40%to about 58%, from about 40%to about 57%, from about 40%to about 56%, from about 40%to about 55%, from about 41%to about 55%, from about 42%to about 55%, from about 43%to about 55%, from about 44%to about 55%, from about 45%to about 55%, from about 43%to about 58%, from about 47%to about 53%, from about 47%to about 57%, from about 45%to about 58%or from about 45%to about 60%by weight, based on the total weight of monomers added in the preparation of the binder composition.
  • the proportion of the carboxylic acid group-containing monomer is less than 70%, less than 69%, less than 68%, less than 67%, less than 66%, less than 65%, less than 64%, less than 63%, less than 62%, less than 61%, less than 60%, less than 59%, less than 58%, less than 57%, less than 56%, less than 55%, less than 54%, less than 53%, less than 52%, less than 51%, less than 50%, less than 49%, less than 48%, less than 47%, less than 46%, less than 45%, less than 44%, less than 43%or less than 42%by weight, based on the total weight of monomers added in the preparation of the binder composition.
  • the proportion of the carboxylic acid group-containing monomer is more than 40%, more than 41%, more than 42%, more than 43%, more than 44%, more than 45%, more than 46%, more than 47%, more than 48%, more than 49%, more than 50%, more than 51%, more than 52%, more than 53%, more than 54%, more than 55%, more than 56%, more than 57%, more than 58%, more than 59%, more than 60%, more than 61%, more than 62%, more than 63%, more than 64%, more than 65%, more than 66%, more than 67%or more than 68%by weight, based on the total weight of monomers added in the preparation of the binder composition.
  • each of the first suspension and the second suspension is independently stirred for a time period of from about 5 minutes to about 45 minutes, from about 5 minutes to about 40 minutes, from about 5 minutes to about 35 minutes, from about 10 minutes to about 35 minutes, from about 15 minutes to about 35 minutes, from about 20 minutes to about 35 minutes or from about 25 minutes to about 35 minutes. In some embodiments, each of the first suspension and the second suspension is independently stirred for a time period of less than 45 minutes, less than 40 minutes, less than 35 minutes, less than 30 minutes, less than 25 minutes, less than 20 minutes, less than 15 minutes or less than 10 minutes.
  • each of the first suspension and the second suspension is independently stirred for a time period of more than 5 minutes, more than 10 minutes, more than 15 minutes, more than 20 minutes, more than 25 minutes, more than 30 minutes, more than 35 minutes or more than 40 minutes.
  • each of the first suspension and the second suspension is independently stirred at a speed of from about 10 rpm to about 600 rpm, from about 10 rpm to about 550 rpm, from about 10 rpm to about 500 rpm, from about 10 rpm to about 450 rpm, from about 10 rpm to about 400 rpm, from about 10 rpm to about 350 rpm, from about 10 rpm to about 300 rpm, from about 10 rpm to about 250 rpm, from about 10 rpm to about 200 rpm, from about 10 rpm to about 180 rpm, from about 10 rpm to about 160 rpm, from about 10 rpm to about 140 rpm, from about 10 rpm to about 120 rpm, from about 10 rpm to about 100 rpm, from about 20 rpm to about 100 rpm, from about 30 rpm to about 100 rpm or from about 40 rpm to about 100 rpm.
  • each of the first suspension and the second suspension is independently stirred at a speed of less than 600 rpm, less than 550 rpm, less than 500 rpm, less than 450 rpm, less than 400 rpm, less than 350 rpm, less than 300 rpm, less than 250 rpm, less than 200 rpm, less than 150 rpm, less than 100 rpm or less than 50 rpm.
  • each of the first suspension and the second suspension is independently stirred at a speed of more than 10 rpm, more than 50 rpm, more than 100 rpm, more than 150 rpm, more than 200 rpm, more than 250 rpm, more than 300 rpm, more than 350 rpm, more than 400 rpm, more than 450 rpm, more than 500 rpm or more than 550 rpm.
  • the temperature of the second suspension is from about 20 °C to about 30 °C, from about 20 °C to about 29 °C, from about 20 °C to about 28 °C, from about 20 °C to about 27 °C, from about 20 °C to about 26 °C, from about 20 °C to about 25 °C, from about 21 °C to about 30 °C, from about 22 °C to about 30 °C, from about 23 °C to about 30 °C, from about 24 °C to about 30 °C, from about 25 °C to about 30 °C, from about 22 °C to about 26 °C or from about 24 °C to about 28 °C.
  • the temperature of the second suspension is less than 30 °C, less than 29 °C, less than 28 °C, less than 27 °C, less than 26 °C, less than 25 °C, less than 24 °C, less than 23 °C, less than 22 °C or less than 21 °C. In some embodiments, the temperature of the second suspension is more than 20 °C, more than 21 °C, more than 22 °C, more than 23 °C, more than 24 °C, more than 25 °C, more than 26 °C, more than 27 °C, more than 28 °C or more than 29 °C.
  • a third suspension is formed by adding an amide group- containing monomer into the second suspension in step 103.
  • a third suspension is formed by adding an amide group-containing monomer solution into the second suspension.
  • the amide group-containing monomer solution can be prepared by dissolving an amide group-containing monomer in water.
  • Structural unit (b) is derived from an amide group-containing monomer. Any monomer that has at least one amide group may be used as amide group-containing monomer without any specific limitations.
  • the amide group-containing monomer is acrylamide, methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, N-n-propyl methacrylamide, N-isopropyl methacrylamide, isopropyl acrylamide, N-n-butyl methacrylamide, N-isobutyl methacrylamide, N, N-dimethyl acrylamide, N, N-dimethyl methacrylamide, N, N-diethyl acrylamide, N, N-diethyl methacrylamide, N-methylol methacrylamide, N- (methoxymethyl) methacrylamide, N- (ethoxymethyl) methacrylamide, N- (propoxymethyl) methacrylamide, N- (butoxymethyl) methacrylamide,
  • the proportion of the amide group-containing monomer is from about 15%to about 35%, from about 15%to about 34%, from about 15%to about 33%, from about 15%to about 32%, from about 15%to about 31%, from about 15%to about 30%, from about 16%to about 30%, from about 17%to about 30%, from about 17%to about 29%, from about 17%to about 28%, from about 17%to about 27%, from about 18%to about 27%, from about 19%to about 27%, from about 20%to about 27%, from 20%to about 25%or from about 15%to about 25%by weight, based on the total weight of monomers added in the preparation of the binder composition.
  • the proportion of the amide-group-containing monomer is less than 35%, less than 34%, less than 33%, less than 32%, less than 31%, less than 30%, less than 29%, less than 28%, less than 27%, less than 26%, less than 25%, less than 24%, less than 23%, less than 22%, less than 21%, less than 20%, less than 19%, less than 18%, less than 17%or less than 16%by weight, based on the total weight of monomers added in the preparation of the binder composition.
  • the proportion of the amide group-containing monomer is more than 15%, more than 16%, more than 17%, more than 18%, more than 19%, more than 20%, more than 21%, more than 22%, more than 23%, more than 24%, more than 25%, more than 26%, more than 27%, more than 28%or more than 29%by weight, based on the total weight of monomers added in the preparation of the binder composition.
  • the third suspension is stirred for a time period of from about 5 minutes to about 60 minutes, from about 5 minutes to about 55 minutes, from about 5 minutes to about 50 minutes, from about 10 minutes to about 50 minutes, from about 15 minutes to about 50 minutes, from about 20 minutes to about 50 minutes, from about 25 minutes to about 50 minutes, from about 30 minutes to about 50 minutes or from about 35 minutes to about 50 minutes. In some embodiments, the third suspension is stirred for a time period of less than 60 minutes, less than 55 minutes, less than 50 minutes, less than 45 minutes, less than 40 minutes, less than 35 minutes, less than 30 minutes, less than 25 minutes, less than 20 minutes, less than 15 minutes or less than 10 minutes.
  • the third suspension is stirred for a time period of more than 5 minutes, more than 10 minutes, more than 15 minutes, more than 20 minutes, more than 25 minutes, more than 30 minutes, more than 35 minutes, more than 40 minutes, more than 45 minutes, more than 50 minutes or more than 55 minutes.
  • the third suspension is stirred at a speed of from about 10 rpm to about 600 rpm, from about 10 rpm to about 550 rpm, from about 10 rpm to about 500 rpm, from about 10 rpm to about 450 rpm, from about 10 rpm to about 400 rpm, from about 10 rpm to about 350 rpm, from about 10 rpm to about 300 rpm, from about 10 rpm to about 250 rpm, from about 10 rpm to about 200 rpm, from about 10 rpm to about 180 rpm, from about 10 rpm to about 160 rpm, from about 10 rpm to about 140 rpm, from about 10 rpm to about 120 rpm, from about 10 rpm to about 100 rpm, from about 20 rpm to about 100 rpm, from about 30 rpm to about 100 rpm or from about 40 rpm to about 100 rpm.
  • the third suspension is stirred at a speed of less than 600 rpm, less than 550 rpm, less than 500 rpm, less than 450 rpm, less than 400 rpm, less than 350 rpm, less than 300 rpm, less than 250 rpm, less than 200 rpm, less than 150 rpm, less than 100 rpm or less than 50 rpm.
  • the third suspension is stirred at a speed of more than 10 rpm, more than 50 rpm, more than 100 rpm, more than 150 rpm, more than 200 rpm, more than 250 rpm, more than 300 rpm, more than 350 rpm, more than 400 rpm, more than 450 rpm, more than 500 rpm or more than 550 rpm.
  • the temperature of the third suspension is elevated to from about 30 °C to about 70 °C, from about 32 °C to about 70 °C, from about 34 °C to about 70 °C, from about 36 °C to about 70 °C, from about 38 °C to about 70 °C, from about 40 °C to about 70 °C, from about 42 °C to about 70 °C, from about 44 °C to about 70 °C, from about 46 °C to about 70 °C, from about 48 °C to about 70 °C or from about 50 °C to about 70 °C.
  • the temperature of the third suspension is elevated to less than 70 °C, less than 68 °C, less than 66 °C, less than 64 °C, less than 62 °C, less than 60 °C, less than 58 °C, less than 56 °C, less than 54 °C, less than 52 °C, less than 50 °C, less than 48 °C, less than 46 °C, less than 44 °C, less than 42 °C, less than 40 °C, less than 38 °C, less than 36 °C or less than 34 °C.
  • the temperature of the third suspension is elevated to more than 30 °C, more than 32 °C, more than 34 °C, more than 36 °C, more than 38 °C, more than 40 °C, more than 42 °C, more than 44 °C, more than 46 °C, more than 48 °C, more than 50 °C, more than 52 °C, more than 54 °C, more than 56 °C, more than 58 °C, more than 60 °C, more than 62 °C, more than 64 °C or more than 66 °C.
  • a fourth suspension is formed by adding a nitrile group-containing monomer into the third suspension in step 104.
  • a fourth suspension is formed by adding a nitrile group-containing monomer solution into the third suspension.
  • the nitrile group-containing monomer solution can be prepared by dissolving a nitrile group-containing monomer in water.
  • Structural unit (c) is derived from a nitrile group-containing monomer. Any monomer that has at least one nitrile group may be used as nitrile group-containing monomer without any specific limitations.
  • the nitrile group-containing monomer include ⁇ , ⁇ -ethylenically unsaturated nitrile monomers.
  • the nitrile group-containing monomer is acrylonitrile, ⁇ -halogenoacrylonitrile, ⁇ -alkylacrylonitrile or a combination thereof.
  • the nitrile group-containing monomer is ⁇ -chloroacrylonitrile, ⁇ -bromoacrylonitrile, ⁇ -fluoroacrylonitrile, methacrylonitrile, ⁇ -ethylacrylonitrile, ⁇ -isopropylacrylonitrile, ⁇ -n-hexylacrylonitrile, ⁇ -methoxyacrylonitrile, 3-methoxyacrylonitrile, 3-ethoxyacrylonitrile, ⁇ -acetoxyacrylonitrile, ⁇ -phenylacrylonitrile, ⁇ -tolylacrylonitrile, ⁇ - (methoxyphenyl) acrylonitrile, ⁇ - (chlorophenyl) acrylonitrile, ⁇ - (cyanophenyl) acrylonitrile, vinylidene cyanide, or a combination thereof.
  • the proportion of the nitrile group-containing monomer is from about 10%to about 24%, from about 10.5%to about 24%, from about 11%to about 24%, from about 11.5%to about 24%, from about 12%to about 24%, from about 12.2%to about 24%, from about 12.4%to about 24%, from about 12.6%to about 24%, from about 12.8%to about 24%, from about 13%to about 24%, from about 13.2%to about 24%, from about 13.4%to about 24%, from about 13.6%to about 24%, from about 13.8%to about 24%, from about 14%to about 24%, from about 14.2%to about 24%, from about 14.4%to about 24%, from about 14.6%to about 24%, from about 14.8%to about 24%, from about 15%to about 24%, from about 15.2%to about 24%, from about 15.4%to about 24%, from about 15.6%to about 24%, from about 15.8%to about 24%, from about 16%to about 24%, from about 16.2%to about 24%, from about 16.4%
  • the proportion of the nitrile group-containing monomer is more than 10%, more than 11%, more than 12%, more than 13%, more than 14%, more than 15%, more than 16%, more than 17%, more than 18%, more than 19%, more than 20%, more than 21%, more than 22%or more than 23%by weight, based on the total weight of monomers added in the preparation of the binder composition.
  • the proportion of the nitrile group-containing monomer is less than 24%, less than 23%, less than 22%, less than 21%, less than 20%, less than 19%, less than 18%, less than 17%, less than 16%, less than 15%, less than 14%, less than 13%, less than 12%or less than 11%by weight, based on the total weight of monomers added in the preparation of the binder composition.
  • combinations of a carboxylic acid group-containing monomer, a nitrile group-containing monomer and an amide group-containing monomer may be added into the first suspension to form a second suspension without forming the third suspension and the fourth suspension.
  • a carboxylic acid group-containing monomer, a nitrile group-containing monomer, an amide group-containing monomer or combinations thereof are added sequentially into the first suspension to form a second suspension, a third suspension or the fourth suspension. Stirring or dispersion may be employed between the additions. This is advantageous as it allows better dispersion of materials. In the case where combinations of monomers are added sequentially, formation of the third suspension or the fourth suspension may be omitted.
  • the fourth suspension is stirred for a time period of from about 5 minutes to about 30 minutes, from about 5 minutes to about 28 minutes, from about 5 minutes to about 26 minutes, from about 5 minutes to about 24 minutes, from about 5 minutes to about 22 minutes, from about 5 minutes to about 20 minutes, from about 5 minutes to about 18 minutes or from about 5 minutes to about 15 minutes. In some embodiments, the fourth suspension is stirred for a time period of less than 30 minutes, less than 28 minutes, less than 26 minutes, less than 24 minutes, less than 22 minutes, less than 20 minutes, less than 18 minutes, less than 16 minutes, less than 14 minutes, less than 12 minutes, less than 10 minutes or less than 8 minutes.
  • the fourth suspension is stirred for a time period of more than 5 minutes, more than 7 minutes, more than 10 minutes, more than 12 minutes, more than 14 minutes, more than 16 minutes, more than 18 minutes, more than 20 minutes, more than 22 minutes, more than 24 minutes, more than 26 minutes or more than 28 minutes.
  • the fourth suspension is stirred at a speed of from about 10 rpm to about 600 rpm, from about 10 rpm to about 550 rpm, from about 10 rpm to about 500 rpm, from about 10 rpm to about 450 rpm, from about 10 rpm to about 400 rpm, from about 10 rpm to about 350 rpm, from about 10 rpm to about 300 rpm, from about 10 rpm to about 250 rpm, from about 10 rpm to about 200 rpm, from about 10 rpm to about 180 rpm, from about 10 rpm to about 160 rpm, from about 10 rpm to about 140 rpm, from about 10 rpm to about 120 rpm, from about 10 rpm to about 100 rpm, from about 20 rpm to about 100 rpm, from about 30 rpm to about 100 rpm or from about 40 rpm to about 100 rpm.
  • the fourth suspension is stirred at a speed of less than 600 rpm, less than 550 rpm, less than 500 rpm, less than 450 rpm, less than 400 rpm, less than 350 rpm, less than 300 rpm, less than 250 rpm, less than 200 rpm, less than 150 rpm, less than 100 rpm or less than 50 rpm.
  • the fourth suspension is stirred at a speed of more than 10 rpm, more than 50 rpm, more than 100 rpm, more than 150 rpm, more than 200 rpm, more than 250 rpm, more than 300 rpm, more than 350 rpm, more than 400 rpm, more than 450 rpm, more than 500 rpm or more than 550 rpm.
  • the copolymer is obtained via polymerization of a composition.
  • the composition comprises a carboxylic salt group-containing monomer, a carboxylic acid group-containing monomer, a nitrile group-containing monomer and an amide group-containing monomer.
  • formation of a carboxylic salt group-containing monomer is resulted from the neutralization of a carboxylic acid group-containing monomer by the neutralizing agent added in step 101.
  • the carboxylic salt group-containing monomer is acrylic acid salt, methacrylic acid salt, crotonic acid salt, 2-butyl crotonic acid salt, cinnamic acid salt, maleic acid salt, maleic anhydride salt, fumaric acid salt, itaconic acid salt, itaconic anhydride salt, tetraconic acid salt or a combination thereof.
  • the carboxylic salt group-containing monomer is 2-ethylacrylic acid salt, isocrotonic acid salt, cis-2-pentenoic acid salt, trans-2-pentenoic acid salt, angelic acid salt, tiglic acid salt, 3, 3-dimethyl acrylic acid salt, 3-propyl acrylic acid salt, trans-2-methyl-3-ethyl acrylic acid salt, cis-2-methyl-3-ethyl acrylic acid salt, 3-isopropyl acrylic acid salt, trans-3-methyl-3-ethyl acrylic acid salt, cis-3-methyl-3-ethyl acrylic acid salt, 2-isopropyl acrylic acid salt, trimethyl acrylic acid salt, 2-methyl-3, 3-diethyl acrylic acid salt, 3-butyl acrylic acid salt, 2-butyl acrylic acid salt, 2-pentyl acrylic acid salt, 2-methyl-2-hexenoic acid salt, trans-3-methyl-2-hexenoic acid salt, 3-methyl-3-propyl acrylic acid salt, 2-ethyl-3-propyl
  • the carboxylic salt group-containing monomer is methyl maleic acid salt, dimethyl maleic acid salt, phenyl maleic acid salt, bromo maleic acid salt, chloromaleic acid salt, dichloromaleic acid salt, fluoromaleic acid salt, difluoro maleic acid salt or a combination thereof.
  • the carboxylic salt group-containing monomer is an alkali metal carboxylic salt group-containing monomer.
  • alkali metal forming the alkali metal carboxylic salt include lithium, sodium and potassium.
  • the carboxylic salt group-containing monomer is an ammonium carboxylic salt group-containing monomer.
  • the molar ratio of the carboxylic acid group-containing monomer to the carboxylic salt group-containing monomer in the composition is from about 0 to about 0.8, from about 0 to about 0.78, from about 0 to about 0.76, from about 0 to about 0.74, from about 0 to about 0.72, from about 0 to about 0.7, from about 0 to about 0.68, from about 0 to about 0.66, from about 0 to about 0.64, from about 0 to about 0.62, from about 0 to about 0.6, from about 0 to about 0.58, from about 0 to about 0.56, from about 0 to about 0.54, from about 0 to about 0.52, from about 0 to about 0.5, from about 0 to about 0.48, from about 0 to about 0.46, from about 0 to about 0.44, from about 0 to about 0.42, from about 0 to about 0.4, from about 0 to about 0.38, from about 0 to about 0.36, from about 0 to about 0.34, from about 0 to about
  • the molar ratio of the carboxylic acid group-containing monomer to the carboxylic salt group-containing monomer in the composition is less than 0.8, less than 0.75, less than 0.7, less than 0.65, less than 0.6, less than 0.55, less than 0.5, less than 0.45, less than 0.4, less than 0.35, less than 0.3, less than 0.25, less than 0.2, less than 0.15, less than 0.1 or less than 0.05.
  • the molar ratio of the carboxylic acid group-containing monomer to the carboxylic salt group-containing monomer in the composition is more than 0, more than 0.05, more than 0.1, more than 0.15, more than 0.2, more than 0.25, more than 0.3, more than 0.35, more than 0.4, more than 0.45, more than 0.5, more than 0.55, more than 0.6, more than 0.65, more than 0.7 or more than 0.75.
  • the proportion of the carboxylic acid group-containing monomer is from about 0%to about 30%, from about 0%to about 29%, from about 0%to about 28%, from about 0%to about 27.5%, from about 0%to about 27%, from about 0%to about 26.5%, from about 0%to about 26%, from about 0%to about 25%, from about 0%to about 24%, from about 0%to about 23%, from about 0%to about 22%, from about 0%to about 21%, from about 0%to about 20%, from about 0%to about 19%, from about 0%to about 18%, from about 0%to about 17%, from about 0%to about 16%, from about 0%to about 15%, from about 1%to about 15%, from about 2%to about 15%, from about 3%to about 15%, from about 4%to about 15%, from about 5%to about 15%, from about 6%to about 15%, from about 6%to about 14%, from about 6%to about 13%, from about 5%to about 20%or from about
  • the proportion of the carboxylic acid group-containing monomer is less than 30%, less than 29%, less than 28%, less than 27%, less than 26%, less than 25%, less than 24%, less than 23%, less than 22%, less than 21%, less than 20%, less than 19%, less than 18%, less than 17%, less than 16%, less than 15%, less than 14%, less than 13%, less than 12%, less than 11%, less than 10%, less than 9%, less than 8%, less than 7%, less than 6%, less than 5%, less than 4%, less than 3%or less than 2%by mole, based on the total number of moles of monomers in the composition.
  • the proportion of the carboxylic acid group-containing monomer is more than 0%, more than 1%, more than 2%, more than 3%, more than 4%, more than 5%, more than 6%, more than 7%, more than 8%, more than 9%, more than 10%, more than 11%, more than 12%, more than 13%, more than 14%, more than 15%, more than 16%, more than 17%, more than 18%, more than 19%, more than 20%, more than 21%, more than 22%, more than 23%, more than 24%, more than 25%, more than 26%, more than 27%or more than 28%by mole, based on the total number of moles of monomers in the composition.
  • the proportion of the carboxylic salt group-containing monomer is from about 25%to about 45%, from about 25.5%to about 45%, from about 26%to about 45%, from about 26.5%to about 45%, from about 27%to about 45%, from about 27.5%to about 45%, from about 28%to about 45%, from about 28.5%to about 45%, from about 29%to about 45%, from about 29.5%to about 45%, from about 30%to about 45%, from about 30%to about 44.5%, from about 30%to about 44%, from about 30%to about 43.5%, from about 30%to about 43%, from about 30%to about 42.5%, from about 30%to about 42%, from about 30%to about 41.5%, from about 30%to about 41%, from about 30%to about 40.5%, from about 30%to about 40%, from about 25%to about 35%or from about 35%to about 40%by mole, based on the total number of moles of monomers in the composition.
  • the proportion of the carboxylic salt group-containing monomer is less than 45%, less than 44%, less than 43%, less than 42%, less than 41%, less than 40%, less than 39%, less than 38%, less than 37%, less than 36%, less than 35%, less than 34%, less than 33%, less than 32%, less than 31%, less than 30%, less than 29%, less than 28%, less than 27%or less than 26%by mole, based on the total number of moles of monomers in the composition.
  • the proportion of the carboxylic salt group-containing monomer is more than 25%, more than 26%, more than 27%, more than 28%, more than 29%, more than 30%, more than 31%, more than 32%, more than 33%, more than 34%, more than 35%, more than 36%, more than 37%, more than 38%or more than 39%by mole, based on the total number of moles of monomers in the composition.
  • the proportion of the nitrile group-containing monomer is from about 10%to about 30%, from about 11%to about 30%, from about 12%to about 30%, from about 13%to about 30%, from about 14%to about 30%, from about 15%to about 30%, from about 16%to about 30%, from about 17%to about 30%, from about 18%to about 30%, from about 19%to about 30%, from about 20%to about 30%, from about 20%to about 29%, from about 20%to about 28%, from about 20%to about 27%, from about 20%to about 26%, from about 20%to about 25%, from about 11%to about 25%, from about 12%to about 25%, from about 13%to about 25%, from about 14%to about 25%, from about 15%to about 25%, from about 16%to about 27%, from about 17%to about 27%, from about 18%to about 27%, from about 19%to about 27%or from about 10%to about 27%by mole, based on the total number of moles of monomers in the composition.
  • the proportion of the nitrile group-containing monomer is less than 30%, less than 29%, less than 28%, less than 27%, less than 26%, less than 25%, less than 24%, less than 23%, less than 22%, less than 21%, less than 20%, less than 19%, less than 18%, less than 17%, less than 16%, less than 15%, less than 14%, less than 13%or less than 12%by mole, based on the total number of moles of monomers in the composition.
  • the proportion of the nitrile group-containing monomer is more than 10%, more than 11%, more than 12%, more than 13%, more than 14%, more than 15%, more than 16%, more than 17%, more than 18%, more than 19%, more than 20%, more than 21%, more than 22%, more than 23%, more than 24%, more than 25%, more than 26%, more than 27%or more than 28%by mole, based on the total number of moles of monomers in the composition.
  • the proportion of the amide group-containing monomer is from about 10%to about 35%, from about 10%to about 34%, from about 10%to about 33%, from about 10%to about 32%, from about 10%to about 31%, from about 10%to about 30%, from about 11%to about 30%, from about 12%to about 30%, from about 13%to about 30%, from about 14%to about 30%, from about 15%to about 30%, from about 16%to about 30%, from about 17%to about 30%, from about 18%to about 30%, from about 19%to about 30%, from about 20%to about 30%, from about 20%to about 29%, from about 20%to about 28%, from about 15%to about 35%or from about 20%to about 35%by mole, based on the total number of moles of monomers in the composition.
  • the proportion of the amide group-containing monomer is less than 35%, less than 34%, less than 33%, less than 32%, less than 31%, less than 30%, less than 29%, less than 28%, less than 27%, less than 26%, less than 25%, less than 24%, less than 23%, less than 22%, less than 21%, less than 20%, less than 18%, less than 16%, less than 14%or less than 12%by mole, based on the total number of moles of monomers in the composition.
  • the proportion of the amide group-containing monomer is more than 10%, more than 11%, more than 12%, more than 13%, more than 14%, more than 15%, more than 16%, more than 17%, more than 18%, more than 19%, more than 20%, more than 21%, more than 22%, more than 23%, more than 24%, more than 25%, more than 26%, more than 27%, more than 28%, more than 29%, more than 30%, more than 32%or more than 34%by mole, based on the total number of moles of monomers in the composition.
  • the initiator solution is prepared by dissolving an initiator in water.
  • a fifth suspension is formed by adding an initiator solution into the fourth suspension in step 105.
  • a fifth suspension is formed by adding portions of the initiator solution sequentially into the fourth suspension. Stirring or dispersion may be employed between the additions.
  • Polymerization occurred in the present invention follows the radical mechanism, wherein an initiator acts to generate free radicals, which in turn lead to polymer chains propagation.
  • the free radicals used herein can be produced using thermal decomposition or redox reactions.
  • the free radical initiator (s) disclosed herein is/are water-soluble.
  • the water-soluble free radical initiator decomposes thermally in the aqueous phase to give radicals which can initiate the polymerization.
  • the water-soluble initiator may be selected from the group consisting of persulfate-based initiators such as ammonium persulfate, sodium persulfate, potassium persulfate and the like; azo-based initiators such as azobis (isobutyl-amidine hydrochloride) (AIBA) , 2, 2'-azobis (2-methylpropionamidine) dihydrochloride, 2, 2-azobis (2-amidinopropane) dihydrochloride (AAPH) , 2, 2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, bis [2- (4′-sulfophenyl) alkyl] -2, 2′-azodiisobutyrate ammonium salts, 2, 2′-azobis (N-2′-methylpropanoyl-2-amino-
  • the water-soluble free radical initiator can be used together with a reducing agent to establish a redox initiator system. This allows generation of free radicals through an oxidation-reduction reaction at relatively low temperatures and promotes an enhancement in polymerization rate.
  • a reducing agent solution is prepared by dissolving the reducing agent in water.
  • the reducing agent can be selected from the group consisting of sodium bisulfite, sodium metabisulfite, sodium sulfite, sodium thiosulfate, thiourea dioxide, ferrous sulfate, ferrous chloride, ascorbic acid, citric acid, tartaric acid, erythorbic acid, glucose and metal salt of formaldehyde sulfoxylate, Bruggolite FF6M combinations thereof.
  • the molar ratio of the water-soluble free radical initiator to the reducing agent is from about 0.2 to about 10, from about 0.2 to about 9, from about 0.2 to about 8, from about 0.2 to about 7, from about 0.2 to about 6, from about 0.2 to about 5, from about 0.3 to about 5, from about 0.4 to about 5, from about 0.5 to about 5, from about 0.6 to about 5, from about 0.7 to about 5, from about 0.8 to about 5, from about 0.9 to about 5, from about 1 to about 5, from about 0.5 to about 4.5, from about 0.5 to about 4, from about 0.6 to about 3.5, from about 0.6 to about 3, from about 0.8 to about 3 or from about 0.2 to about 1.
  • the molar ratio of the water-soluble free radical initiator to the reducing agent is less than 10, less than 9, less than 8, less than 7, less than 6, less than 5, less than 4.8, less than 4.6, less than 4.4, less than 4.2, less than 4, less than 3.8, less than 3.6, less than 3.4, less than 3.2, less than 3, less than 3.8, less than 3.6, less than 3.4, less than 3.2, less than 3, less than 2.8, less than 2.6, less than 2.4, less than 2.2, less than 2, less than 1.8, less than 1.6, less than 1.4, less than 1.2, less than 1, less than 0.8, less than 0.6 or less than 0.4.
  • the molar ratio of the water-soluble free radical initiator to the reducing agent is more than 0.2, more than 0.4, more than 0.6, more than 0.8, more than 1, more than 1.2, more than 1.4, more than 1.6, more than 1.8, more than 2, more than 2.2, more than 2.4, more than 2.6, more than 2.8, more than 3, more than 3.2, more than 3.4, more than 3.6, more than 3.8, more than 4, more than 4.2, more than 4.4, more than 4.6, more than 4.8, more than 5, more than 6, more than 7, more than 8 or more than 9.
  • the polymerization temperature is dependent on the type of initiator applied.
  • the reaction temperature of the polymerization is from about 50 °C to about 90 °C, from about 50 °C to about 85 °C, from about 50 °C to about 80 °C, from about 50 °C to about 75 °C, from about 50 °C to about 70 °C, from about 55 °C to about 75 °C, from about 55 °C to about 80 °C, from about 55 °C to about 85 °C, from about 60 °C to about 80 °C, from about 60 °C to about 75 °C, from about 60 °C to about 70 °C or from about 55 °C to about 70 °C.
  • the reaction temperature of the polymerization is within the above range, a higher reaction stability could be achieved and the binder composition could exhibit a better overall binding performance.
  • the reaction temperature of the polymerization is less than 90 °C, less than 88 °C, less than 86 °C, less than 84 °C, less than 82 °C, less than 80 °C, less than 78 °C, less than 76 °C, less than 74 °C, less than 72 °C, less than 70 °C, less than 68 °C, less than 66 °C, less than 64 °C, less than 62 °C, less than 60 °C, less than 58 °C, less than 56 °Cor less than 54 °C.
  • the reaction temperature of the polymerization is more than 50 °C, more than 52 °C, more than 54 °C, more than 56 °C, more than 58 °C, more than 60 °C, more than 62 °C, more than 64 °C, more than 66 °C, more than 68 °C, more than 70 °C, more than 72 °C, more than 74 °C, more than 76 °C, more than 78 °C, more than 80 °C, more than 82 °C, more than 84 °C or more than 86 °C.
  • the total reaction time of the polymerization is from about 20 hours to about 28 hours, from about 20 hours to about 27.5 hours, from about 20 hours to about 27 hours, from about 20 hours to about 26.5 hours, from about 20 hours to about 26 hours, from about 20.5 hours to about 26 hours, from about 21 hours to about 26 hours, from about 21.5 hours to about 26 hours, from about 22 hours to about 26 hours, from about 22 hours to about 25.5 hours, from about 22 hours to about 25 hours, from about 22.5 hours to about 25 hours, from about 23 hours to about 25 hours, from about 23.5 hours to about 25 hours or from about 23.5 hours to about 24.5 hours.
  • the total reaction time of the polymerization is less than 28 hours, less than 27.5 hours, less than 27 hours, less than 26.5 hours, less than 26 hours, less than 25.5 hours, less than 25 hours, less than 24.5 hours, less than 24 hours, less than 23.5 hours, less than 23 hours, less than 22.5 hours, less than 22 hours, less than 21.5 hours, less than 21 hours or less than 20.5 hours.
  • the total reaction time of the polymerization is more than 20 hours, more than 20.5 hours, more than 21 hours, more than 21.5 hours, more than 22 hours, more than 22.5 hours, more than 23 hours, more than 23.5 hours, more than 24 hours, more than 24.5 hours, more than 25 hours, more than 25.5 hours, more than 26 hours, more than 26.5 hours, more than 27 hours or more than 27.5 hours.
  • the fifth suspension is stirred for a time period of from about 20 hours to about 28 hours, from about 20.25 hours to about 28 hours, from about 20.5 hours to about 28 hours, from about 20.75 hours to about 28 hours, from about 21 hours to about 28 hours, from about 21 hours to about 27.75 hours, from about 21 hours to about 27.5 hours, from about 21 hours to about 27.25 hours, from about 21 hours to about 27 hours, from about 21.25 hours to about 27 hours, from about 21.5 hours to about 27 hours, from about 21.75 hours to about 27 hours, from about 22 hours to about 27 hours, from about 22 hours to about 26.75 hours, from about 22 hours to about 26.5 hours, from about 22 hours to about 26.25 hours, from about 22 hours to about 26 hours, from about 22.25 hours to about 26 hours, from about 22.5 hours to about 26 hours, from about 22.75 hours to about 26 hours, from about 23 hours to about 26 hours, from about 23 hours to about 26 hours, from about 23 hours to about 25.75 hours, from about 23 hours to about 25.5
  • the fifth suspension is stirred for a time period of less than 28 hours, less than 27.5 hours, less than 27 hours, less than 26.5 hours, less than 26 hours, less than 25.5 hours, less than 25 hours, less than 24.5 hours, less than 24 hours, less than 23.5 hours, less than 23 hours, less than 22.5 hours, less than 22 hours, less than 21.5 hours, less than 21 hours or less than 20.5 hours.
  • the fifth suspension is stirred for a time period of more than 20 hours, more than 20.5 hours, more than 21 hours, more than 21.5 hours, more than 22 hours, more than 22.5 hours, more than 23 hours, more than 23.5 hours, more than 24 hours, more than 24.5 hours, more than 25 hours, more than 25.5 hours, more than 26 hours, more than 26.5 hours, more than 27 hours or more than 27.5 hours.
  • the fifth suspension is stirred at a speed of from about 20 rpm to about 300 rpm, from about 20 rpm to about 280 rpm, from about 20 rpm to about 260 rpm, from about 20 rpm to about 240 rpm, from about 20 rpm to about 220 rpm, from about 20 rpm to about 200 rpm, from about 20 rpm to about 180 rpm, from about 20 rpm to about 160 rpm, from about 40 rpm to about 160 rpm, from about 60 rpm to about 160 rpm, from about 60 rpm to about 140 rpm, from about 80 rpm to about 140 rpm, from about 80 rpm to about 120 rpm, from about 50 rpm to about 150 rpm or from about 50 rpm to about 200 rpm.
  • the fifth suspension is stirred at a speed of less than 300 rpm, less than 280 rpm, less than 260 rpm, less than 240 rpm, less than 220 rpm, less than 200 rpm, less than 180 rpm, less than 160 rpm, less than 140 rpm, less than 120 rpm, less than 100 rpm, less than 80 rpm, less than 60 rpm or less than 40 rpm.
  • the fifth suspension is stirred at a speed of more than 20 rpm, more than 40 rpm, more than 60 rpm, more than 80 rpm, more than 100 rpm, more than 120 rpm, more than 140 rpm, more than 160 rpm, more than 180 rpm, more than 200 rpm, more than 220 rpm, more than 240 rpm, more than 260 rpm or more than 280 rpm.
  • the proportion of water-soluble free radical initiator is from about 0.005%to about 0.05%, from about 0.0075%to about 0.05%, from about 0.01%to about 0.05%, from about 0.01%to about 0.048%, from about 0.01%to about 0.046%, from about 0.01%to about 0.044%, from about 0.01%to about 0.042%, from about 0.01%to about 0.04%, from about 0.01%to about 0.038%, from about 0.01%to about 0.036%, from about 0.01%to about 0.034%, from about 0.01%to about 0.032%, from about 0.01%to about 0.03%, from about 0.012%to about 0.03%, from about 0.014%to about 0.03%, from about 0.016%to about 0.03%, from about 0.016%to about 0.028%, from about 0.016%to about 0.026%, from about 0.018%to about 0.026%or from about 0.02%to about 0.026%by weight, based on the total weight of monomers added in the preparation of the bin
  • the proportion of water-soluble free radical initiator is less than 0.05%, less than 0.048%, less than 0.046%, less than 0.044%, less than 0.042%, less than 0.04%, less than 0.038%, less than 0.036%, less than 0.034%, less than 0.032%, less than 0.03%, less than 0.028%, less than 0.026%, less than 0.024%, less than 0.022%, less than 0.02%, less than 0.018%, less than 0.016%, less than 0.014%, less than 0.012%, less than 0.01%, less than 0.008%or less than 0.006%by weight, based on the total weight of monomers added in the preparation of the binder composition.
  • the proportion of water-soluble free radical initiator is more than 0.005%, more than 0.0075%, more than 0.01%, more than 0.012%, more than 0.014%, more than 0.016%, more than 0.018%, more than 0.02%, more than 0.022%, more than 0.024%, more than 0.026%, more than 0.028%, more than 0.03%, more than 0.032%, more than 0.034%, more than 0.036%, more than 0.038%, more than 0.04%, more than 0.042%, more than 0.044%, more than 0.046%or more than 0.048%by weight, based on the total weight of monomers added in the preparation of the binder composition.
  • the proportion of reducing agent is from about 0.001%to about 0.03%, from about 0.0025%to about 0.03%, from about 0.005%to about 0.03%, from about 0.005%to about 0.029%, from about 0.005%to about 0.028%, from about 0.005%to about 0.027%, from about 0.005%to about 0.026%, from about 0.005%to about 0.025%, from about 0.005%to about 0.024%, from about 0.005%to about 0.023%, from about 0.005%to about 0.022%, from about 0.005%to about 0.021%, from about 0.005%to about 0.02%, from about 0.005%to about 0.019%, from about 0.005%to about 0.018%, from about 0.005%to about 0.017%, from about 0.005%to about 0.016%, from about 0.005%to about 0.015%, from about 0.006%to about 0.015%, from about 0.007%to about 0.015%, from about 0.007%to about 0.015%, from about 0.007%to about 0.02%or from about 0.00
  • the proportion of reducing agent is less than 0.03%, less than 0.029%, less than 0.028%, less than 0.027%, less than 0.026%, less than 0.025%, less than 0.024%, less than 0.023%, less than 0.022%, less than 0.021%, less than 0.02%, less than 0.019%, less than 0.018%, less than 0.017%, less than 0.016%, less than 0.015%, less than 0.014%, less than 0.013%, less than 0.012%, less than 0.011%, less than 0.01%, less than 0.008%, less than 0.006%or less than 0.004%by weight, based on the total weight of monomers added in the preparation of the binder composition.
  • the proportion of reducing agent is more than 0.001%, more than 0.0025%, more than 0.005%, more than 0.006%, more than 0.007%, more than 0.008%, more than 0.009%, more than 0.01%, more than 0.011%, more than 0.012%, more than 0.013%, more than 0.014%, more than 0.015%, more than 0.016%, more than 0.017%, more than 0.018%, more than 0.019%, more than 0.02%, more than 0.021%, more than 0.022%, more than 0.023%, more than 0.024%, more than 0.025%, more than 0.026%, more than 0.027%or more than 0.028%by weight, based on the total weight of monomers added in the preparation of the binder composition.
  • a neutralizing solution is prepared by dissolving the neutralizing agent in water.
  • a sixth suspension is formed by adding the neutralizing solution dropwise into the fifth suspension in step 106.
  • the above-mentioned neutralizing agent in step 101 may be selected.
  • the neutralizing agent applied in step 101 may correspond to the neutralizing agent used in step 106.
  • the neutralizing agents applied in steps 101 and 106 may not be the same.
  • the temperature of the fifth suspension is lowered to from about 20 °C to about 40 °C, from about 20 °C to about 39 °C, from about 20 °C to about 38 °C, from about 20 °C to about 37 °C, from about 20 °C to about 36 °C, from about 20 °C to about 35 °C, from about 20 °C to about 34 °C, from about 20 °C to about 33 °C, from about 20 °C to about 32 °C, from about 20 °C to about 31 °C, from about 20 °C to about 30 °C, from about 21 °C to about 35 °C, from about 22 °C to about 35 °C, from about 23 °C to about 35 °C, from about 24 °Cto about 35 °C or from about 25 °C to about 35 °C, prior to adding a neutralizing solution to form a sixth suspension.
  • the temperature of the fifth suspension is lowered to less than 40 °C, less than 39 °C, less than 38 °C, less than 37 °C, less than 36 °C, less than 35 °C, less than 34 °C, less than 33 °C, less than 32 °C, less than 31 °C, less than 30 °C, less than 29 °C, less than 28 °C, less than 27 °C, less than 26 °C, less than 25 °C, less than 24 °C, less than 23 °C, less than 22 °C or less than 21 °C, prior to adding a neutralizing solution to form a sixth suspension.
  • the temperature of the fifth suspension is lowered to more than 20 °C, more than 21 °C, more than 22 °C, more than 23 °C, more than 24 °C, more than 25 °C, more than 26 °C, more than 27 °C, more than 28 °C, more than 29 °C, more than 30 °C, more than 31 °C, more than 32 °C, more than 33 °C, more than 34 °C, more than 35 °C, more than 36 °C, more than 37 °C, more than 38 °C or more than 39 °C, prior to adding a neutralizing solution to form a sixth suspension.
  • the total proportion of the neutralizing agent is from about 35%to about 68%, from about 35%to about 66%, from about 35%to about 64%, from about 35%to about 62%, from about 35%to about 60%, from about 35%to about 59%, from about 35%to about 58%, from about 35%to about 57%, from about 35%to about 56%, from about 35%to about 55%, from about 35%to about 54%, from about 35%to about 53%, from about 35%to about 52%, from about 35%to about 51%, from about 35%to about 50%, from about 36%to about 50%, from about 37%to about 50%, from about 38%to about 50%, from about 39%to about 50%, from about 40%to about 50%, from about 35%to about 45%or from about 42%to about 52%by mole, based on the total number of moles of monomeric units in the copolymer in the binder composition.
  • the total proportion of the neutralizing agent is less than 68%, less than 66%, less than 64%, less than 62%, less than 60%, less than 58%, less than 56%, less than 54%, less than 52%, less than 50%, less than 48%, less than 46%, less than 44%, less than 42%, less than 40%, less than 38%or less than 36%by mole, based on the total number of moles of monomeric units in the copolymer in the binder composition.
  • the total proportion of the neutralizing agent is more than 35%, more than 37%, more than 40%, more than 42%, more than 44%, more than 46%, more than 48%, more than 50%, more than 52%, more than 54%, more than 56%, more than 58%, more than 60%, more than 62%, more than 64%or more than 66%by mole, based on the total number of moles of monomeric units in the copolymer in the binder composition.
  • the neutralizing solution is added dropwise into the fifth suspension for a time period of from about 15 minutes to about 120 minutes, from about 20 minutes to about 120 minutes, from about 30 minutes to about 120 minutes, from about 30 minutes to about 110 minutes, from about 30 minutes to about 100 minutes, from about 30 minutes to about 90 minutes, from about 40 minutes to about 90 minutes, from about 40 minutes to about 80 minutes, from about 45 minutes to about 80 minutes, from about 45 minutes to about 75 minutes, from about 50 minutes to about 75 minutes, from about 50 minutes to about 70 minutes, from about 55 minutes to about 70 minutes or from about 55 minutes to about 65 minutes.
  • the neutralizing solution is added dropwise into the fifth suspension for a time period of less than 120 minutes, less than 110 minutes, less than 100 minutes, less than 90 minutes, less than 80 minutes, less than 70 minutes, less than 60 minutes, less than 50 minutes, less than 40 minutes, less than 30 minutes or less than 20 minutes. In some embodiments, the neutralizing solution is added dropwise into the fifth suspension for a time period of more than 15 minutes, more than 20 minutes, more than 30 minutes, more than 40 minutes, more than 50 minutes, more than 60 minutes, more than 70 minutes or more than 80 minutes.
  • the fifth suspension is stirred for a time period of from about 1 hour to about 6 hours, from about 1 hour to about 5.75 hours, from about 1 hour to about 5.5 hours, from about 1 hour to about 5.25 hours, from about 1 hour to about 5 hours, from about 1 hour to about 4.75 hours, from about 1 hour to about 4.5 hours, from about 1 hour to about 4.25 hours, from about 1 hour to about 4 hours, from about 1.25 hours to about 4 hours, from about 1.5 hours to about 4 hours, from about 1.75 hours to about 4 hours, from about 2 hours to about 4 hours, from about 2.25 hours to about 4 hours, from about 2.5 hours to about 4 hours, from about 2.5 hours to about 3.75 hours, from about 2.5 hours to about 3.5 hours, from about 2.5 hours to about 4 hours or from about 2 hours to about 3.5 hours during the addition of the neutralizing solution and as neutralization takes place.
  • the fifth suspension is stirred for a time period of less than 6 hours, less than 5.75 hours, less than 5.5 hours, less than 5.25 hours, less than 5 hours, less than 4.75 hours, less than 4.5 hours, less than 4.25 hours, less than 4 hours, less than 3.75 hours, less than 3.5 hours, less than 3.25 hours, less than 3 hours, less than 2.75 hours, less than 2.5 hours, less than 2.25 hours, less than 2 hours, less than 1.75 hours or less than 1.5 hours during the addition of the neutralizing solution and as neutralization takes place.
  • the fifth suspension is stirred for a time period of more than 1 hour, more than 1.25 hours, more than 1.5 hours, more than 1.75 hours, more than 2 hours, more than 2.25 hours, more than 2.5 hours, more than 2.75 hours, more than 3 hours, more than 3.25 hours, more than 3.5 hours, more than 3.75 hours, more than 4 hours, more than 4.25 hours, more than 4.5 hours, more than 4.75 hours, more than 5 hours, more than 5.25 hours or more than 5.5 hours during the addition of the neutralizing solution and as neutralization takes place.
  • the fifth suspension is stirred at a speed of from about 20 rpm to about 300 rpm, from about 20 rpm to about 280 rpm, from about 20 rpm to about 260 rpm, from about 20 rpm to about 240 rpm, from about 20 rpm to about 220 rpm, from about 20 rpm to about 200 rpm, from about 20 rpm to about 180 rpm, from about 20 rpm to about 160 rpm, from about 40 rpm to about 160 rpm, from about 60 rpm to about 160 rpm, from about 60 rpm to about 140 rpm, from about 80 rpm to about 140 rpm, from about 80 rpm to about 120 rpm, from about 50 rpm to about 150 rpm or from about 50 rpm to about 200 rpm.
  • the fifth suspension is stirred at a speed of less than 300 rpm, less than 280 rpm, less than 260 rpm, less than 240 rpm, less than 220 rpm, less than 200 rpm, less than 180 rpm, less than 160 rpm, less than 140 rpm, less than 120 rpm, less than 100 rpm, less than 80 rpm, less than 60 rpm or less than 40 rpm.
  • the fifth suspension is stirred at a speed of more than 20 rpm, more than 40 rpm, more than 60 rpm, more than 80 rpm, more than 100 rpm, more than 120 rpm, more than 140 rpm, more than 160 rpm, more than 180 rpm, more than 200 rpm, more than 220 rpm, more than 240 rpm, more than 260 rpm or more than 280 rpm.
  • a binder composition is formed by filtering the sixth suspension in step 107.
  • Additions of neutralizing agents in steps 101 and 106 aims to neutralize the carboxylic acid group-containing monomer added in step 102 in order to produce a binder composition that is slightly alkaline in nature. Exposing binder composition to acidic conditions is undesirable as this may disrupt the dispersion of the binder composition.
  • structural unit (a) derived from a carboxylic acid group-containing monomer comprises a carboxylic salt group.
  • a carboxylic salt group is a salt of a carboxylic acid group.
  • structural unit (a) derived from a carboxylic acid group-containing monomer comprises a combination of a carboxylic salt group and a carboxylic acid group.
  • structural unit (a) comprises an alkali metal carboxylic salt group. Examples of an alkali metal forming the alkali metal carboxylic salt include lithium, sodium and potassium.
  • structural unit (a) comprises an ammonium carboxylic salt group.
  • the molar ratio of the carboxylic acid group to the carboxylic salt group in the copolymer is from about 0 to about 0.2, from about 0 to about 0.19, from about 0 to about 0.18, from about 0 to about 0.17, from about 0 to about 0.16, from about 0 to about 0.15, from about 0 to about 0.14, from about 0 to about 0.13, from about 0 to about 0.12, from about 0 to about 0.11, from about 0 to about 0.1, from about 0 to about 0.09, from about 0 to about 0.08, from about 0 to about 0.07, from about 0 to about 0.06, from about 0 to about 0.05, from about 0.01 to about 0.1, from about 0.02 to about 0.12 or from about 0.01 to about 0.15.
  • the molar ratio of the carboxylic acid group to the carboxylic salt group in the copolymer is less than 0.2, less than 0.19, less than 0.18, less than 0.17, less than 0.16, less than 0.15, less than 0.14, less than 0.13, less than 0.12, less than 0.11, less than 0.1, less than 0.09, less than 0.08, less than 0.07, less than 0.06, less than 0.05, less than 0.04, less than 0.03 or less than 0.02.
  • the molar ratio of the carboxylic acid group to the carboxylic salt group in the copolymer is more than 0, more than 0.01, more than 0.02, more than 0.03, more than 0.04, more than 0.05, more than 0.06, more than 0.07, more than 0.08, more than 0.09, more than 0.1, more than 0.11, more than 0.12, more than 0.13, more than 0.14, more than 0.15, more than 0.16, more than 0.17 or more than 0.18.
  • the proportion of structural unit (a) in the copolymer is from about 33%to about 70%, from about 33%to about 69%, from about 33%to about 68%, from about 33%to about 67%, from about 33%to about 66%, from about 33%to about 65%, from about 33%to about 64%, from about 33%to about 63%, from about 33%to about 62%, from about 33%to about 61%, from about 33%to about 60%, from about 33%to about 59%, from about 33%to about 58%, from about 33%to about 57%, from about 33%to about 56%, from about 33%to about 55%, from about 33%to about 54%, from about 33%to about 53%, from about 33%to about 52%, from about 33%to about 51%, from about 33%to about 50%, from about 34%to about 50%, from about 35%to about 50%, from about 36%to about 50%, from about 37%to about 50%, from about 38%to about 50%, from about 39%to about 50%, from
  • the proportion of structural unit (a) in the copolymer is less than 70%, less than 68%, less than 66%, less than 64%, less than 62%, less than 60%, less than 58%, less than 56%, less than 54%, less than 52%, less than 50%, less than 48%, less than 46%, less than 44%, less than 42%, less than 40%, less than 38%, less than 36%or less than 34%by mole, based on the total number of moles of monomeric units in the copolymer in the binder composition.
  • the proportion of structural unit (a) in the copolymer is more than 33%, more than 34%, more than 36%, more than 38%, more than 40%, more than 42%, more than 44%, more than 46%, more than 48%, more than 50%, more than 52%, more than 54%, more than 56%, more than 58%, more than 60%, more than 62%, more than 64%or more than 66%by mole, based on the total number of moles of monomeric units in the copolymer in the binder composition.
  • the proportion of structural unit (b) in the copolymer is from about 10%to about 35%, from about 10%to about 34%, from about 10%to about 33%, from about 10%to about 32%, from about 10%to about 31%, from about 10%to about 30%, from about 11%to about 30%, from about 12%to about 30%, from about 13%to about 30%, from about 14%to about 30%, from about 15%to about 30%, from about 16%to about 30%, from about 17%to about 30%, from about 18%to about 30%, from about 19%to about 30%, from about 20%to about 30%, from about 20%to about 29%, from about 20%to about 28%, from about 20%to about 27%, from about 20%to about 26%, from about 20%to about 25%, from about 15%to about 28%or from about 15%to about 34%by mole, based on the total number of moles of monomeric units in the copolymer in the binder composition.
  • the proportion of structural unit (b) in the copolymer is less than 35%, less than 34%, less than 33%, less than 32%, less than 31%, less than 30%, less than 29%, less than 28%, less than 27%, less than 26%, less than 25%, less than 24%, less than 23%, less than 22%, less than 21%, less than 20%, less than 19%, less than 18%, less than 17%, less than 16%, less than 15%, less than 14%, less than 13%or less than 12%by mole, based on the total number of moles of monomeric units in the copolymer in the binder composition.
  • the proportion of structural unit (b) in the copolymer is more than 10%, more than 11%, more than 12%, more than 13%, more than 14%, more than 15%, more than 16%, more than 17%, more than 18%, more than 19%, more than 20%, more than 21%, more than 22%, more than 23%, more than 24%, more than 25%, more than 26%, more than 27%, more than 28%, more than 29%, more than 30%, more than 31%, more than 32%or more than 33%by mole, based on the total number of moles of monomeric units in the copolymer in the binder composition.
  • the proportion of structural unit (c) in the copolymer is from about 10%to about 30%, from about 11%to about 30%, from about 12%to about 30%, from about 13%to about 30%, from about 14%to about 30%, from about 15%to about 30%, from about 16%to about 30%, from about 17%to about 30%, from about 18%to about 30%, from about 19%to about 30%, from about 20%to about 30%, from about 20%to about 29%, from about 20%to about 28%, from about 20%to about 27%, from about 20%to about 26%, from about 20%to about 25%, from about 11%to about 25%, from about 12%to about 25%, from about 13%to about 25%, from about 14%to about 25%, from about 15%to about 25%, from about 16%to about 27%, from about 17%to about 27%, from about 18%to about 27%, from about 19%to about 27%or from about 10%to about 27%by mole, based on the total number of moles of monomeric units in the copolymer in the binder composition.
  • the proportion of structural unit (c) in the copolymer is less than 30%, less than 29%, less than 28%, less than 27%, less than 26%, less than 25%, less than 24%, less than 23%, less than 22%, less than 21%, less than 20%, less than 19%, less than 18%, less than 17%, less than 16%, less than 15%, less than 14%, less than 13%or less than 12%by mole, based on the total number of moles of monomeric units in the copolymer in the binder composition.
  • the proportion of structural unit (c) in the copolymer is more than 10%, more than 11%, more than 12%, more than 13%, more than 14%, more than 15%, more than 16%, more than 17%, more than 18%, more than 19%, more than 20%, more than 21%, more than 22%, more than 23%, more than 24%, more than 25%, more than 26%, more than 27%or more than 28%by mole, based on the total number of moles of monomeric units in the copolymer in the binder composition.
  • the proportion of the sum of structural unit (a) and structural unit (c) in the copolymer is from about 65%to about 90%, from about 65%to about 89%, from about 65%to about 88%, from about 65%to about 87%, from about 65%to about 86%, from about 65%to about 85%, from about 65%to about 84%, from about 65%to about 83%, from about 65%to about 82%, from about 65%to about 81%, from about 65%to about 80%, from about 66%to about 80%, from about 67%to about 80%, from about 68%to about 80%, from about 69%to about 80%, from about 70%to about 80%, from about 65%to about 75%or from about 70%to about 85%by mole, based on the total number of moles of monomeric units in the copolymer in the binder composition.
  • the proportion of the sum of structural unit (a) and structural unit (c) in the copolymer is less than 90%, less than 88%, less than 86%, less than 84%, less than 82%, less than 80%, less than 78%, less than 76%, less than 74%, less than 72%, less than 70%, less than 68%or less than 66%by mole, based on the total number of moles of monomeric units in the copolymer in the binder composition.
  • the proportion of the sum of structural unit (a) and structural unit (c) in the copolymer is more than 65%, more than 67%, more than 70%, more than 72%, more than 74%, more than 76%, more than 78%, more than 80%, more than 82%, more than 84%, more than 86%or more than 88%by mole, based on the total number of moles of monomeric units in the copolymer in the binder composition.
  • the molar ratio of the sum of structural unit (a) and structural unit (c) to the structural unit (b) in the copolymer is from about 1 to about 7, from about 1 to about 6.8, from about 1 to about 6.6, from about 1 to about 6.4, from about 1 to about 6.2, from about 1 to about 6, from about 1 to about 5.8, from about 1 to about 5.6, from about 1 to about 5.4, from about 1 to about 5.2, from about 1 to about 5, from about 1 to about 4.8, from about 1 to about 4.6, from about 1 to about 4.4, from about 1 to about 4.2, from about 1 to about 4, from about 1 to about 3.8, from about 1.2 to about 3.8, from about 1.4 to about 3.8, from about 2 to about 6, from about 2 to about 4, from about 3 to about 5 or from about 3 to about 7.
  • the molar ratio of the sum of structural unit (a) and structural unit (c) to the structural unit (b) in the copolymer is less than 7, less than 6.8, less than 6.6, less than 6.4, less than 6.2, less than 6, less than 5.8, less than 5.6, less than 5.4, less than 5.2, less than 5, less than 4.8, less than 4.6, less than 4.4, less than 4.2, less than 4, less than 3.8, less than 3.6, less than 3.4, less than 3.2, less than 3, less than 2.8, less than 2.6, less than 2.4, less than 2.2, less than 2, less than 1.8, less than 1.6, less than 1.4 or less than 1.2.
  • the molar ratio of the sum of structural unit (a) and structural unit (c) to the structural unit (b) in the copolymer is more than 1, more than 1.2, more than 1.4, more than 1.6, more than 1.8, more than 2, more than 2.2, more than 2.4, more than 2.6, more than 2.8, more than 3, more than 3.2, more than 3.4, more than 3.6, more than 3.8, more than 4, more than 4.2, more than 4.4, more than 4.6, more than 4.8, more than 5, more than 5.2, more than 5.4, more than 5.6, more than 5.8, more than 6, more than 6.2, more than 6.4, more than 6.6 or more than 6.8.
  • structural unit (a) and structural unit (b) constitute as the hydrophilic portion of the copolymer. In some embodiments, structural unit (c) constitutes as the hydrophobic portion of the copolymer.
  • the molar ratio of the sum of the structural unit (a) and structural unit (b) to the structural unit (c) in the copolymer is from about 1 to about 7, from about 1 to about 6.8, from about 1 to about 6.6, from about 1 to about 6.4, from about 1 to about 6.2, from about 1 to about 6, from about 1 to about 5.8, from about 1 to about 5.6, from about 1 to about 5.4, from about 1 to about 5.2, from about 1 to about 5, from about 1 to about 4.8, from about 1 to about 4.6, from about 1 to about 4.4, from about 1 to about 4.2, from about 1 to about 4, from about 1 to about 3.8, from about 1 to about 3.6, from about 1 to about 3.4, from about 1.2 to about 3.4, from about 1.4 to about 3.4, from about 1.5 to about 6.7, from about 1.5 to about 5, from about 1.5 to about 4.8 or from about 1.5 to about 4.
  • the molar ratio of the sum of the structural unit (a) and structural unit (b) to the structural unit (c) in the copolymer is less than 7, less than 6.8, less than 6.6, less than 6.4, less than 6.2, less than 6, less than 5.8, less than 5.6, less than 5.4, less than 5.2, less than 5, less than 4.8, less than 4.6, less than 4.4, less than 4.2, less than 4, less than 3.8, less than 3.6, less than 3.4, less than 3.2, less than 3, less than 2.8, less than 2.6, less than 2.4, less than 2.2, less than 2, less than 1.8, less than 1.6, less than 1.4 or less than 1.2.
  • the molar ratio of the sum of the structural unit (a) and structural unit (b) to the structural unit (c) in the copolymer is more than 1, more than 1.2, more than 1.4, more than 1.6, more than 1.8, more than 2, more than 2.2, more than 2.4, more than 2.6, more than 2.8, more than 3, more than 3.2, more than 3.4, more than 3.6, more than 3.8, more than 4, more than 4.2, more than 4.4, more than 4.6, more than 4.8, more than 5, more than 5.2, more than 5.4, more than 5.6, more than 5.8, more than 6, more than 6.2, more than 6.4, more than 6.6 or more than 6.8.
  • the binder composition is free of structural unit derived from an ester group-containing monomer.
  • the ester group-containing monomer is C 1 to C 20 alkyl acrylate, C 1 to C 20 alkyl (meth) acrylate, cycloalkyl acrylate or a combination thereof.
  • the ester group-containing monomer is methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 3, 3, 5-trimethylhexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate, n-tetradecyl acrylate, oxtadecyl acrylate, cyclohexyl acrylate, phenyl acrylate, methoxymethyl acrylate, methoxyethyl acrylate, ethoxymethyl acrylate, ethoxyethyl acrylate, perfluoroocty
  • the ester group-containing monomer is cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, 3, 3, 5-trimethylcyclohexylacrylate, or a combination thereof.
  • the ester group-containing monomer is methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, isopentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, lauryl methacrylate, n-tetradecyl methacrylate, stearyl methacrylate, 2, 2, 2-trifluoroethyl methacrylate, phenyl methacrylate, benzyl methacrylate, or a combination thereof.
  • the binder composition is free of structural unit derived from a conjugated diene group-containing monomer.
  • conjugated diene group-containing monomer include aliphatic conjugated diene monomers such as 1, 3-butadiene, 2-methyl-1, 3-butadiene, 2, 3-dimethyl-1, 3-butadiene, 2-chloro-1, 3-butadiene, substituted linear conjugated pentadienes, and substituted side chain conjugated hexadienes.
  • the binder composition is free of structural unit derived from an aromatic vinyl group-containing monomer.
  • aromatic vinyl group-containing monomer include styrene, ⁇ -methylstyrene, vinyltoluene, and divinylbenzene.
  • the pH of the binder composition is from about 7 to about 9, from about 7 to about 8.9, from about 7 to about 8.8, from about 7 to about 8.7, from about 7 to about 8.6, from about 7 to about 8.5, from about 7 to about 8.4, from about 7 to about 8.3, from about 7 to about 8.2, from about 7 to about 8.1, from about 7 to about 8, from about 7.1 to about 9, from about 7.2 to about 9, from about 7.3 to about 9, from about 7.4 to about 9, from about 7.5 to about 9, from about 7.6 to about 9, from about 7.7 to about 9, from about 7.8 to about 9, from about 7.9 to about 9 or from about 8 to about 9.
  • the pH of the binder composition is less than 9, less than 8.9, less than 8.8, less than 8.7, less than 8.6, less than 8.5, less than 8.4, less than 8.3, less than 8.2, less than 8.1, less than 8, less than 7.9, less than 7.8, less than 7.7, less than 7.6, less than 7.5, less than 7.4, less than 7.3 or less than 7.2.
  • the pH of the binder composition is more than 7, more than 7.1, more than 7.2, more than 7.3, more than 7.4, more than 7.5, more than 7.6, more than 7.7, more than 7.8, more than 7.9, more than 8, more than 8.1, more than 8.2, more than 8.3, more than 8.4, more than 8.5, more than 8.6, more than 8.7 or more than 8.8.
  • the viscosity of the binder composition is from about 10,000 mPa ⁇ s to about 50,000 mPa ⁇ s, from about 10,000 mPa ⁇ s to about 47,500 mPa ⁇ s, from about 10,000 mPa ⁇ s to about 45,000 mPa ⁇ s, from about 10,000 mPa ⁇ s to about 42,500 mPa ⁇ s, from about 10,000 mPa ⁇ s to about 40,000 mPa ⁇ s, from about 10,000 mPa ⁇ s to about 37,500 mPa ⁇ s, from about 10,000 mPa ⁇ s to about 35,000 mPa ⁇ s, from about 10,000 mPa ⁇ s to about 32,500 mPa ⁇ s, from about 10,000 mPa ⁇ s to about 30,000 mPa ⁇ s, from about 10,000 mPa ⁇ s to about 29,000 mPa ⁇ s, from about 10,000 mPa ⁇ s to about 28,000 mPa ⁇ s, from about 10,000 mPa ⁇ s to about 27,000 mPa
  • the viscosity of the binder composition is less than 50,000 mPa ⁇ s, less than 47,500 mPa ⁇ s, less than 45,000 mPa ⁇ s, less than 42,500 mPa ⁇ s, less than 40,000 mPa ⁇ s, less than 37,500 mPa ⁇ s, less than 35,000 mPa ⁇ s, less than 32,500 mPa ⁇ s, less than 30,000 mPa ⁇ s, less than 27,500 mPa ⁇ s, less than 25,000 mPa ⁇ s, less than 22,500 mPa ⁇ s, less than 20,000 mPa ⁇ s, less than 17,500 mPa ⁇ s, less than 15,000 mPa ⁇ sor less than 12,500 mPa ⁇ s.
  • the viscosity of the binder composition is more than 10,000 mPa ⁇ s, more than 12,500 mPa ⁇ s, more than 15,000 mPa ⁇ s, more than 17,500 mPa ⁇ s, more than 20,000 mPa ⁇ s, more than 22,500 mPa ⁇ s, more than 25,000 mPa ⁇ s, more than 27,500 mPa ⁇ s, more than 30,000 mPa ⁇ s, more than 32,500 mPa ⁇ s, more than 35,000 mPa ⁇ s, more than 37,500 mPa ⁇ s, more than 40,000 mPa ⁇ s, more than 42,500 mPa ⁇ s, more than 45,000 mPa ⁇ s, more than 47,500 mPa ⁇ s.
  • the solid content of the binder composition is from about 5%to about 10%, from about 5%to about 9.9%, from about 5%to about 9.8%, from about 5%to about 9.7%, from about 5%to about 9.6%, from about 5%to about 9.5%, from about 5%to about 9.4%, from about 5%to about 9.3%, from about 5%to about 9.2%, from about 5%to about 9.1%, from about 5%to about 9%, from about 5.1%to about 9%, from about 5.2%to about 9%, from about 5.3%to about 9%, from about 5.4%to about 9%, from about 5.5%to about 9%, from about 5.6%to about 9%, from about 5.7%to about 9%, from about 5.8%to about 9%, from about 5.9%to about 9%, from about 6%to about 9%, from about 6%to about 8.9%, from about 6%to about 8.8%, from about 6%to about 8.7%, from about 6%to about 8.6%, from about 6%to about 8.5%, from about 6%to about 8.4%
  • the solid content of the binder composition is less than 10%, less than 9.8%, less than 9.6%, less than 9.4%, less than 9.2%, less than 9%, less than 8.8%, less than 8.6%, less than 8.4%, less than 8.2%, less than 8%, less than 7.8%, less than 7.6%, less than 7.4%, less than 7.2%, less than 7%, less than 6.8%, less than 6.6%, less than 6.4%, less than 6.2%, less than 6%, less than 5.8%, less than 5.6%, less than 5.4%or less than 5.2%by weight, based on the total weight of the binder composition.
  • the solid content of the binder composition is more than 5%, more than 5.2%, more than 5.4%, more than 5.6%, more than 5.8%, more than 6%, more than 6.2%, more than 6.4%, more than 6.6%, more than 6.8%, more than 7%, more than 7.2%, more than 7.4%, more than 7.6%, more than 7.8%, more than 8%, more than 8.2%, more than 8.4%, more than 8.6%, more than 8.8%, more than 9%, more than 9.2%, more than 9.4%, more than 9.6%or more than 9.8%by weight, based on the total weight of the binder composition.
  • the weight average molecular weight of the binder composition is from about 50,000 g/mol to about 200,000 g/mol, from about 55,000 g/mol to about 200,000 g/mol, from about 60,000 g/mol to about 200,000 g/mol, from about 65,000 g/mol to about 200,000 g/mol, from about 70,000 g/mol to about 200,000 g/mol, from about 75,000 g/mol to about 200,000 g/mol, from about 80,000 g/mol to about 200,000 g/mol, from about 85,000 g/mol to about 200,000 g/mol, from about 90,000 g/mol to about 200,000 g/mol, from about 90,000 g/mol to about 190,000 g/mol, from about 90,000 g/mol to about 180,000 g/mol, from about 90,000 g/mol to about 170,000 g/mol, from about 90,000 g/mol to about 160,000 g/mol, from about 95,000 g/mol to
  • weight average molecular weight of the binder composition When the weight average molecular weight of the binder composition is not more than the upper limit set forth above, a smooth binder composition layer can be obtained because coatability of the binder composition is ensured, and adhesive strength of the binder composition can be improved. On the other hand, when the weight average molecular weight of the binder composition is not less than the lower limit set forth above, binding capability of the binder composition can be ensured, and adhesive strength of the binder composition and secondary battery cycle characteristics can be improved.
  • the weight average molecular weight of the binder composition is less than 200,000 g/mol, less than 195,000 g/mol, less than 190,000 g/mol, less than 185,000 g/mol, less than 180,000 g/mol, less than 175,000 g/mol, less than 170,000 g/mol, less than 165,000 g/mol, less than 160,000 g/mol, less than 155,000 g/mol, less than 150,000 g/mol, less than 145,000 g/mol, less than 140,000 g/mol, less than 135,000 g/mol, less than 130,000 g/mol, less than 125,000 g/mol, less than 120,000 g/mol, less than 115,000 g/mol, less than 110,000 g/mol, less than 105,000 g/mol, less than 100,000 g/mol, less than 95,000 g/mol, less than 90,000 g/mol, less than 85,000 g/mol, less than 80,000 g/mol, less than 75,000 g/mol, less
  • the weight average molecular weight of the binder composition is more than 50,000 g/mol, more than 55,000 g/mol, more than 60,000 g/mol, more than 65,000 g/mol, more than 70,000 g/mol, more than 75,000 g/mol, more than 80,000 g/mol, more than 85,000 g/mol, more than 90,000 g/mol, more than 95,000 g/mol, more than 100,000 g/mol, more than 105,000 g/mol, more than 110,000 g/mol, more than 115,000 g/mol, more than 120,000 g/mol, more than 125,000 g/mol, more than 130,000 g/mol, more than 135,000 g/mol, more than 140,000 g/mol, more than 145,000 g/mol, more than 150,000 g/mol, more than 155,000 g/mol, more than 160,000 g/mol, more than 165,000 g/mol, more than 170,000 g/mol, more than 175,000 g/mol, more than 1
  • the number average molecular weight of the binder composition is from about 10,000 g/mol to about 100,000 g/mol, from about 15,000 g/mol to about 100,000 g/mol, from about 20,000 g/mol to about 100,000 g/mol, from about 25,000 g/mol to about 100,000 g/mol, from about 30,000 g/mol to about 100,000 g/mol, from about 35,000 g/mol to about 100,000 g/mol, from about 40,000 g/mol to about 100,000 g/mol, from about 45,000 g/mol to about 100,000 g/mol, from about 50,000 g/mol to about 100,000 g/mol, from about 50,000 g/mol to about 95,000 g/mol, from about 50,000 g/mol to about 90,000 g/mol, from about 50,000 g/mol to about 85,000 g/mol, from about 50,000 g/mol to about 80,000 g/mol, from about 55,000 g/mol to about 80,000 g/mol, from about 60,000 g/mol
  • the number average molecular weight of the binder composition is less than 100,000 g/mol, less than 95,000 g/mol, less than 90,000 g/mol, less than 85,000 g/mol, less than 80,000 g/mol, less than 75,000 g/mol, less than 70,000 g/mol, less than 65,000 g/mol, less than 60,000 g/mol, less than 55,000 g/mol, less than 50,000 g/mol, less than 45,000 g/mol, less than 40,000 g/mol, less than 35,000 g/mol, less than 30,000 g/mol, less than 25,000 g/mol, less than 20,000 g/mol or less than 15,000 g/mol.
  • the number average molecular weight of the binder composition is more than 10,000 g/mol, more than 15,000 g/mol, more than 20,000 g/mol, more than 25,000 g/mol, more than 30,000 g/mol, more than 35,000 g/mol, more than 40,000 g/mol, more than 45,000 g/mol, more than 50,000 g/mol, more than 55,000 g/mol, more than 60,000 g/mol, more than 65,000 g/mol, more than 70,000 g/mol, more than 75,000 g/mol, more than 80,000 g/mol, more than 85,000 g/mol, more than 90,000 g/mol or more than 95,000 g/mol.
  • the polydispersity index (PDI) of the binder composition is from about 1 to about 5, from about 1 to about 4.8, from about 1 to about 4.6, from about 1 to about 4.4, from about 1 to about 4.2, from about 1 to about 4, from about 1 to about 3.8, from about 1 to about 3.6, from about 1 to about 3.4, from about 1 to about 3.2, from about 1 to about 3, from about 1.1 to about 3, from about 1.2 to about 3, from about 1.3 to about 3, from about 1.4 to about 3, from about 1.5 to about 3, from about 1.6 to about 3, from about 1.6 to about 2.8, from about 1.6 to about 2.6, from about 1.8 to about 2.6 or from about 1.8 to about 2.8. Stability of the binder composition can be further improved when the polydispersity index of the binder composition is within the range set forth above.
  • the polydispersity index of the binder composition is less than 5, less than 4.8, less than 4.6, less than 4.4, less than 4.2, less than 4, less than 3.8, less than 3.6, less than 3.4, less than 3.2, less than 3, less than 2.8, less than 2.6, less than 2.4, less than 2.2, less than 2, less than 1.8, less than 1.6, less than 1.4 or less than 1.2.
  • the polydispersity index of the binder composition is more than 1, more than 1.2, more than 1.4, more than 1.6, more than 1.8, more than 2, more than 2.2, more than 2.4, more than 2.6, more than 2.8, more than 3, more than 3.2, more than 3.4, more than 3.6, more than 3.8, more than 4, more than 4.2, more than 4.4, more than 4.6 or more than 4.8.
  • the binder composition of the present invention exhibits strong adhesion to the current collector. It is important for the binder composition to have good adhesive strength to the current collector as it promotes the binding force of the electrode layer to the current collector in the making of battery electrode, prevents separation and enhances the mechanical stability of the electrode.
  • the adhesive strength between the binder composition and the current collector is from about 2 N/cm to about 4 N/cm, from about 2.1 N/cm to about 4 N/cm, from about 2.2 N/cm to about 4 N/cm, from about 2.3 N/cm to about 4 N/cm, from about 2.4 N/cm to about 4 N/cm, from about 2.5 N/cm to about 4 N/cm, from about 2.6 N/cm to about 4 N/cm, from about 2.7 N/cm to about 4 N/cm, from about 2.8 N/cm to about 4 N/cm, from about 2.9 N/cm to about 4 N/cm, from about 3 N/cm to about 4 N/cm, from about 2 N/cm to about 3.9 N/cm, from about 2 N/cm to about 3.8 N/cm, from about 2 N/cm to about 3.7 N/cm, from about 2 N/cm to about 3.6 N/cm,
  • the adhesive strength between the binder composition and the current collector is less than 4 N/cm, less than 3.9 N/cm, less than 3.8 N/cm, less than 3.7 N/cm, less than 3.6 N/cm, less than 3.5 N/cm, less than 3.4 N/cm, less than 3.3 N/cm, less than 3.2 N/cm, less than 3.1 N/cm, less than 3 N/cm, less than 2.9 N/cm, less than 2.8 N/cm, less than 2.7 N/cm, less than 2.6 N/cm, less than 2.5 N/cm, less than 2.4 N/cm, less than 2.3 N/cm or less than 2.2 N/cm.
  • the adhesive strength between the binder composition and the current collector is more than 2 N/cm, more than 2.1 N/cm, more than 2.2 N/cm, more than 2.3 N/cm, more than 2.4 N/cm, more than 2.5 N/cm, more than 2.6 N/cm, more than 2.7 N/cm, more than 2.8 N/cm, more than 2.9 N/cm, more than 3 N/cm, more than 3.1 N/cm, more than 3.2 N/cm, more than 3.3 N/cm, more than 3.4 N/cm, more than 3.5 N/cm, more than 3.6 N/cm, more than 3.7 N/cm or more than 3.8 N/cm.
  • an electrode for a secondary battery comprising an electrode active material, a current collector and the binder composition prepared by the method described above.
  • the electrode further comprises a conductive agent.
  • the electrode active material is a cathode active material, wherein the cathode active material is selected from the group consisting of LiCoO 2 , LiNiO 2 , LiNi x Mn y O 2 , Li 1+z Ni x Mn y Co 1-x-y O 2 , LiNi x Co y Al z O 2, LiV 2 O 5 , LiTiS 2 , LiMoS 2 , LiMnO 2 , LiCrO 2 , LiMn 2 O 4 , Li 2 MnO 3 , LiFeO 2, LiFePO 4, and combinations thereof, wherein each x is independently from 0.2 to 0.9; each y is independently from 0.1 to 0.45; and each z is independently from 0 to 0.2.
  • the cathode active material is selected from the group consisting of LiCoO 2 , LiNiO 2 , LiNi x Mn y O 2 , Li 1+z Ni x Mn y Co 1-x-y O
  • the cathode active material is selected from the group consisting of LiCoO 2 , LiNiO 2 , LiNi x Mn y O 2 , Li 1+z Ni x Mn y Co 1-x-y O 2 (NMC) , LiNi x Co y Al z O 2, LiV 2 O 5 , LiTiS 2 , LiMoS 2 , LiMnO 2 , LiCrO 2 , LiMn 2 O 4 , LiFeO 2, LiFePO 4, and combinations thereof, wherein each x is independently from 0.4 to 0.6; each y is independently from 0.2 to 0.4; and each z is independently from 0 to 0.1.
  • the cathode active material is not LiCoO 2 , LiNiO 2 , LiV 2 O 5 , LiTiS 2 , LiMoS 2 , LiMnO 2 , LiCrO 2 , LiMn 2 O 4 , LiFeO 2, or LiFePO 4 .
  • the cathode active material is not LiNi x Mn y O 2 , Li 1+z Ni x Mn y Co 1-x-y O 2 , or LiNi x Co y Al z O 2, wherein each x is independently from 0.2 to 0.9; each y is independently from 0.1 to 0.45; and each z is independently from 0 to 0.2.
  • the cathode active material is Li 1+x Ni a Mn b Co c Al (1-a-b-c) O 2 ; wherein -0.2 ⁇ x ⁇ 0.2, 0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 1, and a+b+c ⁇ 1.
  • the cathode active material has the general formula Li 1+x Ni a Mn b Co c Al (1-a-b-c) O 2 , with 0.33 ⁇ a ⁇ 0.92, 0.33 ⁇ a ⁇ 0.9, 0.33 ⁇ a ⁇ 0.8, 0.5 ⁇ a ⁇ 0.92, 0.5 ⁇ a ⁇ 0.9, 0.5 ⁇ a ⁇ 0.8, 0.6 ⁇ a ⁇ 0.92, or 0.6 ⁇ a ⁇ 0.9; 0 ⁇ b ⁇ 0.5, 0 ⁇ b ⁇ 0.3, 0.1 ⁇ b ⁇ 0.5, 0.1 ⁇ b ⁇ 0.4, 0.1 ⁇ b ⁇ 0.3, 0.1 ⁇ b ⁇ 0.2, or 0.2 ⁇ b ⁇ 0.5; 0 ⁇ c ⁇ 0.5, 0 ⁇ c ⁇ 0.3, 0.1 ⁇ c ⁇ 0.5, 0.1 ⁇ c ⁇ 0.4, 0.1 ⁇ c ⁇ 0.3, 0.1 ⁇ c ⁇ 0.2, or 0.2 ⁇ c ⁇ 0.5.
  • the cathode active material is doped with a dopant selected from the group consisting of Fe, Ni, Mn, Al, Mg, Zn, Ti, La, Ce, Sn, Zr, Ru, Si, Ge, and combinations thereof.
  • the dopant is not Fe, Ni, Mn, Mg, Zn, Ti, La, Ce, Ru, Si, or Ge.
  • the dopant is not Al, Sn, or Zr.
  • the cathode active material is LiNi 0.33 Mn 0.33 Co 0.33 O 2 (NMC333) , LiNi 0.4 Mn 0.4 Co 0.2 O 2 , LiNi 0.5 Mn 0.3 Co 0.2 O 2 (NMC532) , LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) , LiNi 0.7 Mn 0.15 Co 0.15 O 2 , LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) , LiNi 0.92 Mn 0.04 Co 0.04 O 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA) , LiNiO 2 (LNO) , and combinations thereof.
  • NMC333 LiNi 0.33 Mn 0.33 Co 0.33 O 2
  • NMC532 LiNi 0.4 Mn 0.4 Co 0.2 O 2
  • NMC622 LiNi 0.6 Mn 0.2 Co 0.2 O 2
  • NMC811
  • the cathode active material is not LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , or Li 2 MnO 3 .
  • the cathode active material is not LiNi 0.33 Mn 0.33 Co 0.33 O 2 , LiNi 0.4 Mn 0.4 Co 0.2 O 2 , LiNi 0.5 Mn 0.3 Co 0.2 O 2 , LiNi 0.6 Mn 0.2 Co 0.2 O 2 , LiNi 0.7 Mn 0.15 Co 0.15 O 2 , LiNi 0.8 Mn 0.1 Co 0.1 O 2 , LiNi 0.92 Mn 0.04 Co 0.04 O 2 , or LiNi 0.8 Co 0.15 Al 0.05 O 2 .
  • the cathode active material comprises or is a core-shell composite having a core and shell structure, wherein the core and the shell each independently comprise a lithium transition metal oxide selected from the group consisting of Li 1+x Ni a Mn b Co c Al (1-a-b-c) O 2 , LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , Li 2 MnO 3 , LiCrO 2 , Li 4 Ti 5 O 12 , LiV 2 O 5 , LiTiS 2 , LiMoS 2 , and combinations thereof; wherein -0.2 ⁇ x ⁇ 0.2, 0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 1, and a+b+c ⁇ 1.
  • the core and the shell each independently comprise two or more lithium transition metal oxides.
  • one of the core or shell comprises only one lithium transition metal oxide, while the other comprises two or more lithium transition metal oxides.
  • the lithium transition metal oxide or oxides in the core and the shell may be the same, or they may be different or partially different.
  • the two or more lithium transition metal oxides are uniformly distributed over the core.
  • the two or more lithium transition metal oxides are not uniformly distributed over the core.
  • the cathode active material is not a core-shell composite.
  • each of the lithium transition metal oxides in the core and the shell is independently doped with a dopant selected from the group consisting of Fe, Ni, Mn, Al, Mg, Zn, Ti, La, Ce, Sn, Zr, Ru, Si, Ge, and combinations thereof.
  • the core and the shell each independently comprise two or more doped lithium transition metal oxides.
  • the two or more doped lithium transition metal oxides are uniformly distributed over the core and/or the shell. In certain embodiments, the two or more doped lithium transition metal oxides are not uniformly distributed over the core and/or the shell.
  • the cathode active material comprises or is a core-shell composite comprising a core comprising a lithium transition metal oxide and a shell comprising a transition metal oxide.
  • the lithium transition metal oxide is selected from the group consisting of Li 1+x Ni a Mn b Co c Al (1-a-b-c) O 2 , LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , Li 2 MnO 3 , LiCrO 2 , Li 4 Ti 5 O 12 , LiV 2 O 5 , LiTiS 2 , LiMoS 2 , and combinations thereof; wherein -0.2 ⁇ x ⁇ 0.2, 0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 1, and a+b+c ⁇ 1.
  • the transition metal oxide is selected from the group consisting of Fe 2 O 3 , MnO 2 , Al 2 O 3 , MgO, ZnO, TiO 2 , La 2 O 3 , CeO 2 , SnO 2 , ZrO 2 , RuO 2 , and combinations thereof.
  • the shell comprises a lithium transition metal oxide and a transition metal oxide.
  • the diameter of the core is from about 1 ⁇ m to about 15 ⁇ m, from about 3 ⁇ m to about 15 ⁇ m, from about 3 ⁇ m to about 10 ⁇ m, from about 5 ⁇ m to about 10 ⁇ m, from about 5 ⁇ m to about 45 ⁇ m, from about 5 ⁇ m to about 35 ⁇ m, from about 5 ⁇ m to about 25 ⁇ m, from about 10 ⁇ m to about 45 ⁇ m, from about 10 ⁇ m to about 40 ⁇ m, or from about 10 ⁇ m to about 35 ⁇ m, from about 10 ⁇ m to about 25 ⁇ m, from about 15 ⁇ m to about 45 ⁇ m, from about 15 ⁇ m to about 30 ⁇ m, from about 15 ⁇ m to about 25 ⁇ m, from about 20 ⁇ m to about 35 ⁇ m, or from about 20 ⁇ m to about 30 ⁇ m.
  • the thickness of the shell is from about 1 ⁇ m to about 45 ⁇ m, from about 1 ⁇ m to about 35 ⁇ m, from about 1 ⁇ m to about 25 ⁇ m, from about 1 ⁇ m to about 15 ⁇ m, from about 1 ⁇ m to about 10 ⁇ m, from about 1 ⁇ m to about 5 ⁇ m, from about 3 ⁇ m to about 15 ⁇ m, from about 3 ⁇ m to about 10 ⁇ m, from about 5 ⁇ m to about 10 ⁇ m, from about 10 ⁇ m to about 35 ⁇ m, from about 10 ⁇ m to about 20 ⁇ m, from about 15 ⁇ m to about 30 ⁇ m, from about 15 ⁇ m to about 25 ⁇ m, or from about 20 ⁇ m to about 35 ⁇ m.
  • the diameter or thickness ratio of the core and the shell are in the range of 15: 85 to 85: 15, 25: 75 to 75: 25, 30: 70 to 70: 30, or 40: 60 to 60: 40.
  • the volume or weight ratio of the core and the shell is 95: 5, 90: 10, 80: 20, 70: 30, 60: 40, 50: 50, 40: 60, or 30: 70.
  • the current collector acts to collect electrons generated by electrochemical reactions of the cathode active material or to supply electrons required for the electrochemical reactions.
  • the current collector can be in the form of a foil, sheet or film.
  • the current collector is stainless steel, titanium, nickel, aluminum, copper, or alloys thereof or electrically-conductive resin.
  • the current collector has a two-layered structure comprising an outer layer and an inner layer, wherein the outer layer comprises a conductive material and the inner layer comprises an insulating material or another conductive material; for example, aluminum mounted with a conductive resin layer or a polymeric insulating material coated with an aluminum film.
  • the current collector has a three-layered structure comprising an outer layer, a middle layer and an inner layer, wherein the outer and inner layers comprise a conductive material and the middle layer comprises an insulating material or another conductive material; for example, a plastic substrate coated with a metal film on both sides.
  • each of the outer layer, middle layer and inner layer is independently stainless steel, titanium, nickel, aluminum, copper, or alloys thereof or electrically-conductive resin.
  • the insulating material is a polymeric material selected from the group consisting of polycarbonate, polyacrylate, polyacrylonitrile, polyester, polyamide, polystyrene, polyurethane, polyepoxy, poly (acrylonitrile butadiene styrene) , polyimide, polyolefin, polyethylene, polypropylene, polyphenylene sulfide, poly (vinyl ester) , polyvinyl chloride, polyether, polyphenylene oxide, cellulose polymer and combinations thereof.
  • the current collector has more than three layers.
  • the current collector is coated with a protective coating.
  • the protective coating comprises a carbon-containing material.
  • the current collector is not coated with a protective coating.
  • the thickness of the current collector affects the volume it occupies within the battery, the amount of the electrode active material needed, and hence the capacity in the battery.
  • the current collector has a thickness from about 5 ⁇ m to about 30 ⁇ m. In certain embodiments, the current collector has a thickness from about 5 ⁇ m to about 20 ⁇ m, from about 5 ⁇ m to about 15 ⁇ m, from about 10 ⁇ m to about 30 ⁇ m, from about 10 ⁇ m to about 25 ⁇ m, or from about 10 ⁇ m to about 20 ⁇ m.
  • the current collector has a thickness of less than 30 ⁇ m, less than 28 ⁇ m, less than 26 ⁇ m, less than 24 ⁇ m, less than 22 ⁇ m, less than 20 ⁇ m, less than 18 ⁇ m, less than 16 ⁇ m, less than 14 ⁇ m, less than 12 ⁇ m, less than 10 ⁇ m, less than 8 ⁇ m or less than 6 ⁇ m.
  • the current collector has a thickness of more than 5 ⁇ m, more than 7 ⁇ m, more than 10 ⁇ m, more than 12 ⁇ m, more than 14 ⁇ m, more than 16 ⁇ m, more than 18 ⁇ m, more than 20 ⁇ m, more than 22 ⁇ m, more than 24 ⁇ m, more than 26 ⁇ m or more than 28 ⁇ m.
  • the conductive agent is for enhancing the electrically-conducting property of an electrode. Any suitable material can act as the conductive agent.
  • the conductive agent is a carbonaceous material. Some non-limiting examples include carbon, carbon black, graphite, expanded graphite, graphene, graphene nanoplatelets, carbon fibers, carbon nano-fibers, graphitized carbon flake, carbon tubes, activated carbon, Super P, 0-dimensional KS6, 1-dimensional vapor grown carbon fibers (VGCF) , mesoporous carbon and combinations thereof.
  • the cathode prepared using the binder composition in the present invention exhibits strong adhesion of the electrode layer to the current collector. It is important for the electrode layer to have good peeling strength to the current collector as this prevents delamination or separation of the electrode, which would greatly influence the mechanical stability of the electrodes and the cyclability of the battery. Therefore, the electrodes should have sufficient peeling strength to withstand the rigors of battery manufacture.
  • the peeling strength between the current collector and the electrode layer is in the range from about 1.0 N/cm to about 8.0 N/cm, from about 1.0 N/cm to about 6.0 N/cm, from about 1.0 N/cm to about 5.0 N/cm, from about 1.0 N/cm to about 4.0 N/cm, from about 1.0 N/cm to about 3.0 N/cm, from about 1.0 N/cm to about 2.5 N/cm, from about 1.0 N/cm to about 2.0 N/cm, from about 1.2 N/cm to about 3.0 N/cm, from about 1.2 N/cm to about 2.5 N/cm, from about 1.2 N/cm to about 2.0 N/cm, from about 1.5 N/cm to about 3.0 N/cm, from about 1.5 N/cm to about 2.5 N/cm, from about 1.5 N/cm to about 2.0 N/cm, from about 1.8 N/cm to about 3.0 N/cm, from about 1.8 N/cm to
  • the peeling strength between the current collector and the electrode layer is 1.0 N/cm or more, 1.2 N/cm or more, 1.5 N/cm or more, 2.0 N/cm or more, 2.2 N/cm or more, 2.5 N/cm or more, 3.0 N/cm or more, 3.5 N/cm or more, 4.5 N/cm or more, 5.0 N/cm or more, 5.5 N/cm or more.
  • the peeling strength between the current collector and the electrode layer is less than 6.5 N/cm, less than 6.0 N/cm, less than 5.5 N/cm, less than 5.0 N/cm, less than 4.5 N/cm, less than 4.0 N/cm, less than 3.5 N/cm, less than 3.0 N/cm, less than 2.8 N/cm, less than 2.5 N/cm, less than 2.2 N/cm, less than 2.0 N/cm, less than 1.8 N/cm, or less than 1.5 N/cm.
  • the extent of swelling of the binder composition from an uptake of electrolyte in the secondary battery provides insight into the crystallinity of the binder composition, how the binder composition interacts with the electrolyte and the flexibility of the binder composition.
  • a binder composition of high crystallinity exhibits low swelling behavior that can act as barriers for solvent ingress, provides shorter ion transport pathways, thus reduces internal resistance and more importantly alter the mechanical properties of the swollen polymer, which are critical to stable battery performance.
  • a binder composition of low crystallinity has a higher amount of amorphous regions where higher amounts of electrolyte can penetrate into the binder composition to ensure good ion transport without the binder composition breaking apart when subjected to expansion.
  • a semi-crystalline binder composition disclosed herein benefits from both influence factors and therefore demonstrates exceptional electrochemical performance.
  • the electrolyte swelling of the binder composition is from about 7%to about 10%, from about 7%to about 9.9%, from about 7%to about 9.8%, from about 7%to about 9.7%, from about 7%to about 9.6%, from about 7%to about 9.5%, from about 7%to about 9.4%, from about 7%to about 9.3%, from about 7%to about 9.2%, from about 7%to about 9.1%, from about 7%to about 9%, from about 7%to about 8.9%, from about 7%to about 8.8%, from about 7%to about 8.7%, from about 7%to about 8.6%, from about 7%to about 8.5%, from about 7%to about 8.4%, from about 7%to about 8.3%, from about 7%to about 8.2%, from about 7%to about 8.1%, from about 7%to about 8%, from about 7.1%to about 10%, from about 7.2%to about 10%, from about 7.3%to about 10%, from about 7.4%to about 10%, from about 7.5%to about 10%, from about 7.6%to about 10%, from about
  • the electrolyte swelling of the binder composition is less than 10%, less than 9.9%, less than 9.8%, less than 9.7%, less than 9.6%, less than 9.5%, less than 9.4%, less than 9.3%, less than 9.2%, less than 9.1%, less than 8%, less than 8.9%, less than 8.8%, less than 8.7%, less than 8.6%, less than 8.5%, less than 8.4%, less than 8.3%, less than 8.2%, less than 8.1%, less than 8%, less than 7.9%, less than 7.8%, less than 7.7%, less than 7.6%, less than 7.5%, less than 7.4%, less than 7.3%, less than 7.2%or less than 7.1%.
  • the electrolyte swelling of the binder composition is more than 7%, more than 7.1%, more than 7.2%, more than 7.3%, more than 7.4%, more than 7.5%, more than 7.6%, more than 7.7%, more than 7.8%, more than 7.9%, more than 8%, more than 8.1%, more than 8.2%, more than 8.3%, more than 8.4%, more than 8.5%, more than 8.6%, more than 8.7%, more than 8.8%, more than 8.9%, more than 9%, more than 9.1%, more than 9.2%, more than 9.3%, more than 9.4%, more than 9.5%, more than 9.6%, more than 9.7%, more than 9.8%or more than 9.9%.
  • the method disclosed herein has the advantage that aqueous solvents can be used in the manufacturing process, which can save on processing time and equipment, as well as improve safety by eliminating the need to handle or recycle hazardous organic solvents.
  • costs are reduced by simplifying the overall process. Therefore, this method is especially suited for industrial processes because of its low cost and ease of handling.
  • the pH values of the binder composition were measured by an electrode-type pH meter (ION 2700, Eutech Instruments) .
  • the viscosities of the binder composition were measured using a rotational viscosity meter (NDJ-5S, Shanghai JT Electronic Technology Co. Ltd., China) at 25 °C.
  • the adhesive strengths of the dried binder composition layers were measured by a tensile testing machine (DZ-106A, obtained from Dongguan Zonhow Test Equipment Co. Ltd., China) . This test measures the average force required to peel a binder composition layer from the current collector at 180° angle in Newtons.
  • the mean roughness depth (R z ) of the current collector is 2 ⁇ m.
  • the binder composition was coated on the current collector and dried to obtain a binder composition layer of thickness 10 ⁇ m to 12 ⁇ m. The coated current collector was then placed in an environment of constant temperature of 25 °C and humidity of 50%to 60%for 30 minutes.
  • a strip of adhesion tape (3M; US; model no.
  • the binder composition strip was clipped onto the testing machine and the tape was folded back on itself at 180 degrees, and placed in a moveable jaw and pulled at room temperature and a peel rate of 300 mm per minute. The maximum stripping force measured was taken as the adhesive strength. Measurements were repeated three times to find the average value.
  • the electrolyte swelling of the binder composition measures the extent of mass change of binder composition before and after electrolyte soaking.
  • Test samples of dried binder composition strips with a length of 50 mm to 60 mm and a width of 1 mm were prepared.
  • the dried binder composition strips were further dried at 80 °C for 1 to 2 hours to completely remove the moisture in the strips.
  • the weights of the dried binder composition strips were measured and the strips were placed in a sealed container with electrolyte after cooling.
  • the binder composition strips were soaked in the electrolyte at 25 °C for 3 days. After removing the binder composition strips from the electrolyte-containing container, the electrolyte on the surface of the strips were absorbed with oil-absorbing papers.
  • the weights of the soaked binder composition strips were measured.
  • the electrolyte swelling is the ratio of the weight change of the strip before and after electrolyte soaking to the weight of the strip before electrolyte soaking. Measurements were repeated three times to find the average value.
  • the solid content of the binder composition measures the extent of mass change of binder composition before and after drying. Approximately 1 g of a binder composition was weighed in a weighing bottle and dried at 110 ⁇ 5°C and -0.09 MPa for more than 5 hours by a vacuum dryer. The binder composition was cooled in a desiccator for about 15 minutes and then measured in terms of mass. The difference in mass of the binder composition before and after the drying was determined, and the solid content (%) of the binder composition was calculated according to the following formula:
  • the weight average molecular weight and number average molecular weight of the binder composition were measured by gel permeation chromatography (GPC) .
  • the binder composition was firstly dissolved in dimethylformamide at room temperature. Once dissolution of the binder composition was completed, the solution was gently filtered through a 0.45 ⁇ m filter to prepare a measurement sample.
  • a standard polystyrene was used to prepare a calibration curve such that the weight average molecular weight and the number average molecular weight were calculated as standard substance equivalent values.
  • the distribution of molecular weights in the binder composition is described by the Polydispersity Index (PDI) that is the ratio of the weight average molecular weight to the number average molecular weight.
  • PDI Polydispersity Index
  • AM acrylamide
  • AN acrylonitrile
  • 0.075 g of water-soluble free radical initiator (ammonium persulfate, APS; obtained from Aladdin Industries Corporation, China) was dissolved in 15 g of DI water and 0.0375 g of reducing agent (sodium bisulfite; obtained from Tianjin Damao Chemical Reagent Factory, China) was dissolved in 7.5 g of DI water. 15.075 g of APS solution and 7.5375 g of sodium bisulfite solution were added into the fourth suspension. The mixture was stirred at 200 rpm for 24 h at 55 °C to obtain a fifth suspension.
  • APS ammonium persulfate
  • reducing agent sodium bisulfite
  • the temperature of the fifth suspension was lowered to 25 °C. 19.12 g of NaOH was dissolved in 3300 g of DI water. Thereafter, 3319.12 g of sodium hydroxide solution was added dropwise into the fifth suspension for 1 h to adjust pH to 7.59 to form the sixth suspension.
  • the binder composition was furnished by filtration using 200 mesh filter paper.
  • the solid content of the binder composition was 6.77 wt. %.
  • the weight average molecular weight, the number average molecular weight and the polydispersity index of the binder composition were 125,031 g/mol, 55,437 g/mol and 2.26 respectively.
  • the components of the binder composition of Example 1 and their respective proportions are shown in Table 1 below.
  • the pH, solid content, viscosity, adhesive strength and electrolyte swelling of the binder composition of Example 1 were measured and are shown in Table 2 below.
  • a first mixture was prepared by dispersing 0.9 g of conductive agent (SuperP; obtained from Timcal Ltd, Bodio, Switzerland) and 6 g of binder composition (6.77 wt. %solid content) in 7.4 g of deionized water while stirring with an overhead stirrer (R20, IKA) . After the addition, the first mixture was further stirred for about 30 minutes at 25 °C at a speed of 1,200 rpm.
  • conductive agent SuperP
  • binder composition (6.77 wt. %solid content
  • a second mixture was prepared by adding 28.2 g of NMC622 (obtained from Shandong Tianjiao New Energy Co., Ltd, China) in the first mixture at 25 °C while stirring with an overhead stirrer. Then, the second mixture was degassed under a pressure of about 10 kPa for 1 hour. Then, the second mixture was further stirred for about 60 minutes at 25 °C at a speed of 1,200 rpm to form a homogenized slurry.
  • NMC622 obtained from Shandong Tianjiao New Energy Co., Ltd, China
  • the homogenized slurry was coated onto one side of an aluminum foil having a thickness of 14 ⁇ m as a current collector using a doctor blade coater.
  • the coated slurry film on the aluminum foil was dried at about 85 °C for 120 minutes by a hot air dryer (DHG 10H, Huyue Equipment Co., Ltd., China) to form a cathode electrode layer.
  • the electrode was then pressed to decrease the thickness of the cathode electrode layer to 27 ⁇ m and the surface density was 5.2 mg/cm 2 .
  • a negative electrode slurry was prepared by mixing 90 wt. %of hard carbon (BTR New Energy Materials Inc., Shenzhen, Guangdong, China) with 1.5 wt. %carboxymethyl cellulose (CMC, BSH-12, DKS Co. Ltd., Japan) and 3.5 wt. %SBR (AL-2001, NIPPON A&L INC., Japan) as a binder, and 5 wt. %carbon black as a conductive agent in deionized water.
  • the solid content of the anode slurry was 50 wt. %.
  • the slurry was coated onto one side of a copper foil having a thickness of 8 ⁇ m using a doctor blade coater. The coated film on the copper foil was dried at about 85 °C for 120 minutes by a hot air dryer to obtain a negative electrode. The electrode was then pressed to decrease the thickness of the coating to 18 ⁇ m.
  • CR2032 coin-type Li cells were assembled in an argon-filled glove box.
  • the coated cathode and anode sheets were cut into disc-form positive and negative electrodes, which were then assembled into an electrode assembly by stacking the cathode and anode electrode plates alternatively and then packaged in a case made of stainless steel of the CR2032 type.
  • the cathode and anode electrode plates were kept apart by separators.
  • the separator was a ceramic coated microporous membrane made of nonwoven fabric (MPM, Japan) , which had a thickness of about 25 ⁇ m.
  • the electrode assembly was then dried in a box-type resistance oven under vacuum (DZF-6020, obtained from Shenzhen Kejing Star Technology Co. Ltd., China) at 105 °C for about 16 hours.
  • the electrolyte was then injected into the case holding the packed electrodes under a high-purity argon atmosphere with a moisture and oxygen content of less than 3 ppm respectively.
  • the electrolyte was a solution of LiPF 6 (1 M) in a mixture of ethylene carbonate (EC) , ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC) at a volume ratio of 1: 1: 1.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • the coin cells were analyzed in a constant current mode using a multi-channel battery tester (BTS-4008-5V10mA, obtained from Neware Electronics Co. Ltd, China) . After 1 cycle at C/20 was completed, they were charged and discharged at a rate of C/2. The charging/discharging cycling tests of the cells were performed between 3.0 and 4.3 V at a current density of C/2 at 25 °C to obtain the discharge capacity.
  • the electrochemical performance of the coin cell of Example 1 was measured and is shown in Table 2 below.
  • 0.015 g of APS was dissolved in 3 g of DI water and 0.0075 g of sodium bisulfite was dissolved in 1.5 g of DI water. 3.015 g of APS solution and 1.5075 g of sodium bisulfite solution were added into the fourth suspension. The mixture was stirred at 200 rpm for 24 h at 55 °C to obtain a fifth suspension.
  • the temperature of the fifth suspension was lowered to 25 °C. 3.72 g of NaOH was dissolved in 400 g of DI water. Thereafter, 403.72 g of sodium hydroxide solution was added dropwise into the fifth suspension for 1 h to adjust pH to 7.31 to form the sixth suspension.
  • the binder composition was furnished by filtration using 200 mesh filter paper. The solid content of the binder composition was 9.00 wt. %.
  • Example 3 A binder composition was prepared in the same manner as in Example 2, except that 36.04 g of AA was added in the preparation of the second suspension, 17.0 g of AM was added in the preparation of the third suspension and 14.96 g of AN was added in the preparation of the fourth suspension.
  • Example 4 A binder composition was prepared in the same manner as in Example 2, except that 37.4 g of AA was added in the preparation of the second suspension, 17.0 g of AM was added in the preparation of the third suspension and 13.6 g of AN was added in the preparation of the fourth suspension.
  • Example 5 A binder composition was prepared in the same manner as in Example 2, except that 40.8 g of AA was added in the preparation of the second suspension, 17.0 g of AM was added in the preparation of the third suspension, 10.2 g of AN was added in the preparation of the fourth suspension and 5.33 g of NaOH was added in the preparation of the sixth suspension.
  • Example 6 A binder composition was prepared in the same manner as in Example 2, except that 44.2 g of AA was added in the preparation of the second suspension, 17.0 g of AM was added in the preparation of the third suspension, 6.8 g of AN was added in the preparation of the fourth suspension and 6.23 g of NaOH was added in the preparation of the sixth suspension.
  • Example 7 A binder composition was prepared in the same manner as in Example 2, except that 47.6 g of AA was added in the preparation of the second suspension, 10.2 g of AM was added in the preparation of the third suspension, 10.2 g of AN was added in the preparation of the fourth suspension and 8.18 g of NaOH was added in the preparation of the sixth suspension.
  • Example 8 A binder composition was prepared in the same manner as in Example 2, except that 28.56 g of AA was added in the preparation of the second suspension, 23.12 g of AM was added in the preparation of the third suspension and 16.32 g of AN was added in the preparation of the fourth suspension.
  • Example 9 A binder composition was prepared in the same manner as in Example 2, except that 34.0 g of AA was added in the preparation of the second suspension, 23.8 g of AM was added in the preparation of the third suspension and 10.2 g of AN was added in the preparation of the fourth suspension.
  • Example 10 A binder composition was prepared in the same manner as in Example 2, except that 9.50 g of NaOH was added into the fifth suspension to adjust pH to 8.23 in the preparation of the sixth suspension.
  • Example 11 A binder composition was prepared in the same manner as in Example 2, except that 10.93 g of NaOH was added into the fifth suspension to adjust pH to 8.51 in the preparation of the sixth suspension.
  • Example 15 A binder composition was prepared in the same manner as in Example 2, except that 0.0204 g of APS was dissolved in 3 g of DI water and 0.0102 g of sodium bisulfite was dissolved in 1.5 g of DI water so that 3.0204 g of APS solution and 1.5102 g of sodium bisulfite solution were added in the preparation of the fifth suspension.
  • the weight average molecular weight, the number average molecular weight and the polydispersity index of the binder composition were 78, 528 g/mol, 33, 523 g/mol and 2.34 respectively.
  • Example 16 A binder composition was prepared in the same manner as in Example 2, except that 0.0068 g of APS was dissolved in 3 g of DI water and 0.0034 g of sodium bisulfite was dissolved in 1.5 g of DI water so that 3.0068 g of APS solution and 1.5034 g of sodium bisulfite solution were added in the preparation of the fifth suspension.
  • the weight average molecular weight, the number average molecular weight and the polydispersity index of the binder composition were 175,432 g/mol, 82,640 g/mol and 2.12 respectively.
  • a binder composition was prepared in the same manner as in Example 2, except that 30.6 g of AA was added in the preparation of the second suspension, 10.2 g of AM was added in the preparation of the third suspension and 27.2 g of AN was added in the preparation of the fourth suspension.
  • a binder composition was prepared in the same manner as in Example 2, except that 44.2 g of AA was added in the preparation of the second suspension, 20.4 g of AM was added in the preparation of the third suspension, 3.4 g of AN was added in the preparation of the fourth suspension and 6.5 g of NaOH was added in the preparation of the sixth suspension.
  • a binder composition was prepared in the same manner as in Example 2, except that 51.0 g of AA was added in the preparation of the second suspension, 10.2 g of AM was added in the preparation of the third suspension, 6.8 g of AN was added in the preparation of the fourth suspension and 10.42 g of NaOH was added in the preparation of the sixth suspension.
  • a binder composition was prepared in the same manner as in Example 2, except that 46.92 g of AA was added in the preparation of the second suspension, 5.44 g of AM was added in the preparation of the third suspension, 15.64 g of AN was added in the preparation of the fourth suspension and 8.23 g of NaOH was added in the preparation of the sixth suspension.
  • a binder composition was prepared in the same manner as in Example 2, except that 30.6 g of AA was added in the preparation of the second suspension, 30.6 g of AM was added in the preparation of the third suspension and 6.8 g of AN was added in the preparation of the fourth suspension.
  • a binder composition was prepared in the same manner as in Example 2, except that 8 g of NaOH was added in the preparation of the first suspension, 20.4 g of AA was added in the preparation of the second suspension, 31.96 g of AM was added in the preparation of the third suspension, 15.64 g of AN was added in the preparation of the fourth suspension and 3.21 g of NaOH was added in the preparation of the sixth suspension.
  • a binder composition was prepared in the same manner as in Example 2, except that 5 g of NaOH was added in the preparation of the first suspension, 13.6 g of AA was added in the preparation of the second suspension, 27.2 g of AM was added in the preparation of the third suspension, 27.2 g of AN was added in the preparation of the fourth suspension and 2.1 g of NaOH was added in the preparation of the sixth suspension.
  • a binder composition was prepared in the same manner as in Example 2, except that 57.8 g of AA was added in the preparation of the second suspension, 6.8 g of AM was added in the preparation of the third suspension, 3.4 g of AN was added in the preparation of the fourth suspension and 13.5 g of NaOH was added in the preparation of the sixth suspension.
  • a binder composition was prepared in the same manner as in Example 2, except that 34.0 g of AA and 6.8 g of methyl acrylate (MA) were added in the preparation of the second suspension, 13.6 g of AM was added in the preparation of the third suspension, 13.6 g of AN was added in the preparation of the fourth suspension and 3.72 g of NaOH was added in the preparation of the sixth suspension.
  • MA methyl acrylate
  • a binder composition was prepared in the same manner as in Example 2, except that 34.0 g of AA was added in the preparation of the second suspension, 14.96 g of AM was added in the preparation of the third suspension and 19.04 g of AN was added in the preparation of the fourth suspension.
  • Example 12 The positive electrode of Example 12 was prepared in the same manner as in Example 1, except that the 28.2 g of NMC622 was replaced with NMC532 (obtained from Tianjin Bamo Technology Co., Ltd., China) of the same weight.
  • the positive electrode of Example 13 was prepared in the same manner as in Example 1, except that the 28.2 g of NMC622 was replaced with LiCoO 2 (obtained from Tianjin Bamo Technology Co., Ltd., China) of the same weight.
  • the positive electrode of Example 14 was prepared in the same manner as in Example 1, except that the 28.2 g of NMC622 was replaced with LiFePO 4 (obtained from Xiamen Tungsten Industry Co., Ltd., China) of the same weight.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne une composition de liant aqueuse pour une électrode de batterie secondaire, qui comprend un copolymère et un milieu de dispersion, le copolymère comprenant une unité structurale (a) dérivée d'un monomère contenant un groupe acide carboxylique, une unité structurale (b) dérivée d'un monomère contenant un groupe amide et une unité structurale (c) dérivée d'un monomère contenant un groupe nitrile, avec une capacité de liaison améliorée. De plus, des cellules de batterie comprenant la cathode préparée à l'aide de la composition de liant de l'invention présentent une performance électrochimique exceptionnelle.
PCT/CN2020/117789 2020-03-20 2020-09-25 Composition de liant pour batterie secondaire WO2021253675A1 (fr)

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KR1020227046323A KR20230028734A (ko) 2020-06-17 2020-09-25 2차 전지용 바인더 조성물
US17/910,813 US20230121093A1 (en) 2020-06-17 2020-09-25 Binder composition for secondary battery
CA3183233A CA3183233A1 (fr) 2020-06-17 2020-09-25 Composition de liant pour batterie secondaire
CN202080062552.9A CN114342125B (zh) 2020-06-17 2020-09-25 用于二次电池的粘结剂组合物
EP20940735.2A EP4104221A1 (fr) 2020-06-17 2020-09-25 Composition de liant pour batterie secondaire
CN202410295012.5A CN118016892A (zh) 2020-06-17 2020-09-25 用于二次电池的粘结剂组合物
JP2022562146A JP2023529531A (ja) 2020-06-17 2020-09-25 二次電池用バインダー組成物
AU2020453243A AU2020453243A1 (en) 2020-06-17 2020-09-25 Binder composition for secondary battery
AU2020453945A AU2020453945A1 (en) 2020-06-17 2020-12-25 Method for composite delamination
KR1020227043316A KR20230025778A (ko) 2020-06-17 2020-12-25 복합체 박리 방법
CN202080067229.0A CN114503336B (zh) 2020-06-17 2020-12-25 复合物的剥离方法
PCT/CN2020/139555 WO2021253787A1 (fr) 2020-06-17 2020-12-25 Procédé de délaminage de composite
CA3183236A CA3183236A1 (fr) 2020-06-17 2020-12-25 Procede de delaminage de composite
JP2022568795A JP7516557B2 (ja) 2020-06-17 2020-12-25 複合材剥離方法
EP20941173.5A EP4169108A4 (fr) 2020-06-17 2020-12-25 Procédé de délaminage de composite
US17/912,038 US20230138359A1 (en) 2020-06-17 2020-12-25 Method for composite delamination
PCT/CN2020/141488 WO2021253796A1 (fr) 2020-06-17 2020-12-30 Composition de pâte pour électrode souple dans batterie secondaire
KR1020237001858A KR102712570B1 (ko) 2020-06-17 2021-02-10 폴리머 침전 방법
CA3183237A CA3183237A1 (fr) 2020-06-17 2021-02-10 Procede de precipitation de polymere
EP21825136.1A EP4169095A4 (fr) 2020-06-17 2021-02-10 Procédé de précipitation de polymère
AU2021291911A AU2021291911A1 (en) 2020-06-17 2021-02-10 Method for polymer precipitation
CN202180007279.4A CN114846654B (zh) 2020-06-17 2021-02-10 用于使聚合物沉淀的方法
US17/914,367 US20230105056A1 (en) 2020-06-17 2021-02-10 Method for polymer precipitation
PCT/CN2021/076466 WO2021253849A1 (fr) 2020-06-17 2021-02-10 Procédé de précipitation de polymère
JP2022578586A JP2023530012A (ja) 2020-06-17 2021-02-10 複合材剥離方法
CN202180005210.8A CN114424365B (zh) 2020-03-20 2021-03-12 用于二次电池的阴极及阴极浆料
KR1020227034091A KR102719375B1 (ko) 2020-03-20 2021-03-12 2차 전지용 양극 및 양극 슬러리
CN202410220707.7A CN118099430A (zh) 2020-03-20 2021-03-12 用于二次电池的阴极及阴极浆料
US17/797,116 US20230073006A1 (en) 2020-03-20 2021-03-12 Cathode and cathode slurry for secondary battery
CA3183234A CA3183234A1 (fr) 2020-03-20 2021-03-12 Cathode et suspension de cathode pour batterie secondaire
EP21771882.4A EP4088331A1 (fr) 2020-03-20 2021-03-12 Cathode et suspension de cathode pour batterie secondaire
PCT/CN2021/080568 WO2021185183A1 (fr) 2020-03-20 2021-03-12 Cathode et suspension de cathode pour batterie secondaire
JP2022555710A JP2023517376A (ja) 2020-03-20 2021-03-12 二次電池のための、カソードおよびカソードスラリー
US17/922,380 US20230175095A1 (en) 2020-06-17 2021-03-15 Method for composite delamination
EP21827044.5A EP4169110A4 (fr) 2020-06-17 2021-03-15 Procédé de délaminage de composite
PCT/CN2021/080684 WO2021253887A1 (fr) 2020-06-17 2021-03-15 Procédé de délaminage de composite
PCT/CN2021/080683 WO2021253886A1 (fr) 2020-06-17 2021-03-15 Procédé de délaminage de composite
US17/916,590 US20230340379A1 (en) 2020-06-17 2021-03-15 Method for composite delamination
PCT/CN2021/080682 WO2021253885A1 (fr) 2020-06-17 2021-03-15 Procédé de délaminage de composite
PCT/CN2021/080670 WO2021253883A1 (fr) 2020-06-17 2021-03-15 Procédé de délaminage de composite
CN202180011083.2A CN115023843A (zh) 2020-06-17 2021-03-15 复合物的剥离方法
US17/923,925 US20230178820A1 (en) 2020-06-17 2021-03-15 Method for composite delamination
PCT/CN2021/080685 WO2021253888A1 (fr) 2020-06-17 2021-03-15 Procédé de délaminage de composite
JP2022577450A JP2023530345A (ja) 2020-06-17 2021-03-15 複合材料の剥離方法
US17/923,239 US20230182462A1 (en) 2020-06-17 2021-03-15 Method for composite delamination
CN202180011327.7A CN115023844A (zh) 2020-06-17 2021-03-15 复合物的剥离方法
PCT/CN2021/080681 WO2021253884A1 (fr) 2020-06-17 2021-03-15 Procédé de délaminage de composite
KR1020227046218A KR20230025806A (ko) 2020-06-17 2021-03-15 복합체 박리 방법
US17/917,949 US20230136670A1 (en) 2020-06-17 2021-03-15 Method for composite delamination
CN202180024380.0A CN115336085A (zh) 2020-06-17 2021-03-15 复合物的剥离方法
JP2022572495A JP2023529583A (ja) 2020-06-17 2021-03-15 複合材料の剥離方法
KR1020227046182A KR20230025412A (ko) 2020-06-17 2021-03-15 복합체 박리 방법
CN202180012653.XA CN115053380A (zh) 2020-06-17 2021-03-15 复合物的剥离方法
CN202180013075.1A CN115053381A (zh) 2020-06-17 2021-03-15 复合物的剥离方法
EP21825583.4A EP4118704A4 (fr) 2020-06-17 2021-03-15 Procédé de délaminage de composite
TW110110085A TW202143536A (zh) 2020-03-20 2021-03-19 用於二次電池的陰極及陰極漿料
AU2021290598A AU2021290598A1 (en) 2020-06-17 2021-06-01 Method for composite delamination
JP2022571743A JP2023530075A (ja) 2020-06-17 2021-06-01 複合材料の剥離方法
PCT/CN2021/097669 WO2021254138A1 (fr) 2020-06-17 2021-06-01 Procédé de délaminage de composite
US17/915,493 US20230198039A1 (en) 2020-06-17 2021-06-01 Method for composite delamination
KR1020227046178A KR20230025805A (ko) 2020-06-17 2021-06-01 복합체 박리 방법
EP21826097.4A EP4169106A4 (fr) 2020-06-17 2021-06-01 Procédé de délaminage de composite
CA3183238A CA3183238A1 (fr) 2020-06-17 2021-06-01 Procede de delaminage de composite
CN202180007275.6A CN114868298A (zh) 2020-06-17 2021-06-01 复合物的剥离方法
US17/912,851 US20230142072A1 (en) 2020-06-17 2021-06-03 Slurry composition for flexible electrode in secondary battery
PCT/CN2021/098036 WO2021254157A1 (fr) 2020-06-17 2021-06-03 Composition de bouillie pour électrode flexible dans une batterie secondaire
CN202180006980.4A CN114762152B (zh) 2020-06-17 2021-06-03 用于二次电池中柔韧电极的浆料组合物
CN202180006979.1A CN114762145A (zh) 2020-06-17 2021-06-03 用于二次电池中柔韧电极的浆料组合物
PCT/CN2021/098037 WO2021254158A1 (fr) 2020-06-17 2021-06-03 Composition de pâte pour électrode souple dans batterie secondaire
US17/925,607 US20230207813A1 (en) 2020-06-17 2021-06-03 Slurry composition for flexible electrode in secondary battery
KR1020237001934A KR20230025707A (ko) 2020-06-17 2021-06-08 2차 전지용 캐소드 활물질, 캐소드 슬러리 및 캐소드
CN202180032081.1A CN115668547A (zh) 2020-06-17 2021-06-08 用于二次电池的阴极活性材料、阴极浆料和阴极
KR1020237002041A KR20230027206A (ko) 2020-06-17 2021-06-08 2차 전지용 캐소드 활물질, 캐소드 슬러리 및 캐소드
US17/925,836 US20230187639A1 (en) 2020-06-17 2021-06-08 Cathode active material, cathode slurry and cathode for secondary battery
PCT/CN2021/098918 WO2021254215A1 (fr) 2020-06-17 2021-06-08 Matériau actif de cathode, bouillie de cathode et cathode pour batterie rechargeable
JP2022577317A JP2023529987A (ja) 2020-06-17 2021-06-08 正極活物質、正極スラリーおよび二次電池用正極
JP2022575181A JP2023529661A (ja) 2020-06-17 2021-06-08 正極活物質、正極スラリーおよび二次電池用正極
PCT/CN2021/098950 WO2021254218A1 (fr) 2020-06-17 2021-06-08 Matériau actif de cathode, bouillie de cathode et cathode pour batterie rechargeable
EP21827079.1A EP4169098A1 (fr) 2020-06-17 2021-06-08 Matériau actif de cathode, bouillie de cathode et cathode pour batterie rechargeable
CN202180032063.3A CN115568289A (zh) 2020-06-17 2021-06-08 用于二次电池的阴极活性材料、阴极浆料和阴极
EP21826609.6A EP4143905A1 (fr) 2020-06-17 2021-06-08 Matériau actif de cathode, bouillie de cathode et cathode pour batterie rechargeable
US17/926,995 US20230223517A1 (en) 2020-06-17 2021-06-08 Cathode active material, cathode slurry and cathode for secondary battery
JP2022576796A JP2023530929A (ja) 2020-06-17 2021-06-10 二次電池用バインダ組成物
CN202180024379.8A CN115380096A (zh) 2020-06-17 2021-06-10 用于二次电池的粘结剂组合物
EP21824876.3A EP4136182A1 (fr) 2020-06-17 2021-06-10 Composition de liant pour batterie secondaire
CA3183239A CA3183239A1 (fr) 2020-06-17 2021-06-10 Composition de liant pour batterie secondaire
AU2021292254A AU2021292254A1 (en) 2020-06-17 2021-06-10 Binder composition for secondary battery
KR1020227046166A KR20230024297A (ko) 2020-06-17 2021-06-10 이차 전지용 바인더 조성물
PCT/CN2021/099368 WO2021254245A1 (fr) 2020-06-17 2021-06-10 Composition de liant pour batterie secondaire
US17/924,375 US20230178740A1 (en) 2020-06-17 2021-06-10 Binder composition for secondary battery
TW110121751A TW202211529A (zh) 2020-06-17 2021-06-15 複合物的剝離方法
AU2021291990A AU2021291990A1 (en) 2020-06-17 2021-06-15 Binder composition for secondary battery
TW110121754A TW202200641A (zh) 2020-06-17 2021-06-15 用於二次電池的黏結劑組合物
TW110121755A TW202200393A (zh) 2020-06-17 2021-06-15 複合物的剝離方法
JP2022577379A JP2023530330A (ja) 2020-06-17 2021-06-15 二次電池用バインダー組成物
KR1020237001859A KR20230027194A (ko) 2020-06-17 2021-06-15 2차 전지용 바인더 조성물
PCT/CN2021/099950 WO2021254300A1 (fr) 2020-06-17 2021-06-15 Composition de liant pour batterie secondaire
TW110121758A TW202201830A (zh) 2020-06-17 2021-06-15 用於二次電池中柔韌電極的漿料組合物
TW110121756A TW202200394A (zh) 2020-06-17 2021-06-15 複合物的剝離方法
CN202180036152.5A CN115668549A (zh) 2020-06-17 2021-06-15 用于二次电池的粘结剂组合物
TW110121757A TW202200395A (zh) 2020-06-17 2021-06-15 複合物的剝離方法
CA3183240A CA3183240A1 (fr) 2020-06-17 2021-06-15 Composition de liant pour batterie secondaire
US17/927,750 US20230216055A1 (en) 2020-06-17 2021-06-15 Binder composition for secondary battery
EP21827012.2A EP4169097A4 (fr) 2020-06-17 2021-06-15 Composition de liant pour batterie secondaire
TW110121967A TW202200396A (zh) 2020-06-17 2021-06-16 複合物的剝離方法
PCT/CN2021/100365 WO2021254393A1 (fr) 2020-06-17 2021-06-16 Procédé de recyclage d'électrodes de batterie
TW110121972A TW202201835A (zh) 2020-06-17 2021-06-16 用於二次電池的黏結劑組合物
TW110121973A TW202207506A (zh) 2020-06-17 2021-06-16 用於二次電池的陰極活性材料、陰極漿料和陰極
US18/007,753 US20230299372A1 (en) 2020-06-17 2021-06-16 Method for recycling battery electrodes
AU2021290702A AU2021290702A1 (en) 2020-06-17 2021-06-16 Method for recycling battery electrodes
EP21826301.0A EP4169109A4 (fr) 2020-06-17 2021-06-16 Procédé de recyclage d'électrodes de batterie
TW110121966A TW202211523A (zh) 2020-06-17 2021-06-16 用於二次電池的黏結劑組合物
TW110121974A TW202211525A (zh) 2020-06-17 2021-06-16 用於二次電池的陰極活性材料、陰極漿料和陰極
CA3183241A CA3183241A1 (fr) 2020-06-17 2021-06-16 Procede de recyclage d'electrodes de batterie
TW110121971A TW202211524A (zh) 2020-06-17 2021-06-16 用於二次電池中柔韌電極的漿料組合物
CN202180041284.7A CN115885408A (zh) 2020-06-17 2021-06-16 回收电池电极的方法
TW110121968A TW202200397A (zh) 2020-06-17 2021-06-16 複合物的剝離方法
JP2022577316A JP2023529986A (ja) 2020-06-17 2021-06-16 電池電極のリサイクル方法
KR1020237002049A KR20230027207A (ko) 2020-06-17 2021-06-16 전지 전극 재활용 방법
TW110121969A TW202200398A (zh) 2020-06-17 2021-06-16 複合物的剝離方法
TW110121970A TW202210530A (zh) 2020-06-17 2021-06-16 用於使聚合物沉澱的方法
TW110122185A TW202220271A (zh) 2020-06-17 2021-06-17 回收電池電極的方法

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PCT/CN2020/096672 WO2021253302A1 (fr) 2020-06-17 2020-06-17 Composition conductrice pour batterie secondaire
CNPCT/CN2020/096672 2020-06-17
PCT/CN2020/110065 WO2021253615A1 (fr) 2020-06-17 2020-08-19 Composition de liant pour batterie secondaire
PCT/CN2020/110105 WO2021253616A1 (fr) 2020-06-17 2020-08-19 Composition de liant pour batterie secondaire
CNPCT/CN2020/110105 2020-08-19
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