• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:
    anode for secondary battery and secondary battery including the same. the present invention discloses an anode for secondary batteries and a secondary battery including the same. the anode includes an anode mixture including an anode active material, coated onto a current collector, wherein the anode active material includes lithium-titanium (lto) oxide particles provided on the surfaces thereof with a cross-linked polymer coating layer , wherein the lto particles with the crosslinked polymer coating layer formed thereon maintain a porous structure formed therebetween, and a crosslinked polymer of the coating layer is a phosphate-based compound.
    公开号:BR112014031293B1
    申请号:R112014031293-1
    申请日:2013-07-10
    公开日:2021-07-13
    发明作者:Kyoung-Ho Ahn；Chul-Haeng Lee；Doo-Kyung Yang；Min-Jung Kim；Jung-Hoon Lee；Yi-Jin Jung
    申请人:Lg Chem, Ltd .；
    IPC主号:
    专利说明:

    Technical Field
    [001] The present invention relates to an anode for secondary batteries in which an anode mixture including an anode active material is coated on a current collector, in which the anode active material includes lithium-titanium oxide particles (LTO) provided on a surface thereof with a cross-linked polymer coating layer, wherein the LTO particles with the cross-linked polymer coating layer formed on them have a porous structure formed between them, and a cross-linked polymer of the coating layer is a phosphate-based compound and a secondary battery including the same. Fundamentals of Technique
    [002]As mobile device technology continues to develop and demand for it continues to increase, the demand for secondary batteries as power sources is growing rapidly. Among these secondary batteries, lithium secondary batteries, which exhibit high energy density and operating potential, have long cycle life expectancy, and have a low self-discharge rate, are commercially available and are widely used.
    [003] In addition, as recent interest in environmental issues is growing, research into electric vehicles (EVs), hybrid electric vehicles (HEVs), and the like that can replace vehicles using fossil fuels, such as gasoline vehicles, vehicles diesel, and the like, which are one of the main causes behind air pollution, is on its way. As a power supply for EVs, HEVs, and the like, a nickel-metal hydride (Ni-MH) secondary battery is primarily used. However, research into secondary lithium batteries having high energy density, high discharge voltage, and high output stability is actively carried out and some of the secondary lithium batteries are commercially available.
    [004] A secondary lithium battery has a structure in which an electrode assembly, which includes: a cathode prepared by coating a cathode active material over a cathode current collector; an anode prepared by coating an anode active material onto an anode current collector; and a porous separator disposed between the cathode and the anode, is impregnated with a non-aqueous electrolyte containing no lithium salt.
    [005] Such secondary lithium batteries require a certain or higher level of porosity of an electrode in consideration of the ionic conductivity of active materials.
    [006] However, the excess reduction in porosity of an electrode occurs in a process of preparing an electrode slurry including an active electrode material and, consequently, the rapid decrease in the C rate can be caused.
    [007] Secondary batteries require a certain level or higher of C rating according to individual applications, and in particular, secondary batteries for power tools that require high power batteries or secondary batteries for EVs and HEVs require C rating much louder.
    [008]Therefore, there is an urgent need to develop a technology that can address the problems described above. Disclosure Technical problem
    [009] Therefore, the present invention was made to solve the above problems and other technical problems that have yet to be solved.
    [010]As a result of a variety of extensive and intensive studies and experiments, the inventors of the present invention have confirmed that when lithium-titanium oxide, a surface of which is coated with a phosphate-based compound as a crosslinked polymer, is used as an anode active material, desired effects can be obtained, thus completing the present invention. Technical Solution
    [011] According to one aspect of the present invention, an anode is provided for secondary batteries in which an anode mixture including an anode active material is coated onto a current collector, wherein the anode active material includes particles of lithium-titanium oxide (LTO) provided on a surface thereof with a crosslinked polymer coating layer, wherein the LTO particles with the crosslinked polymer coating layer formed thereon maintain a porous structure formed between them, and a Cross-linked polymer coating layer is a phosphate-based compound.
    [012] The anode according to the present invention uses LTO, a surface of which is coated with a phosphate-based compound, as an anode active material and thus can enhance energy production characteristics and can also enhance expectation of life due to a stabilized electrode interface.
    [013] In particular, LTO particles maintain a predetermined porous structure even though the coating layer is formed on the surfaces of the LTO particles, and thus, a specific surface area of a layer of active anode material can be increased and the connectivity between the pores can be enhanced and, consequently, an impregnation ratio of an electrolyte can be increased, which results in enhanced charge and discharge characteristics.
    [014]That is, the phosphate-based compound has high reactivity with radicals and thus is considered to enhance the electrochemical stability of the anode active material by improving the progress of polymerization.
    [015]In particular, an LTO electrode can accelerate the electrolyte decomposition reaction (Ti4+<—^ Ti3+) during charging and discharging and saline anions can accelerate LTO catalytic and electrochemical reactions. In these aspects, it is considered that a phosphate group can reduce the decomposition of liquid electrolyte by binding to Ti3+ with high stability and reduction reactivity through binding with anions and also serve to suppress the structural decomposition of the formed film.
    [016] In addition, LTO used as an anode active material acts as a catalyst and thus can accelerate the crosslinking polymerization of the phosphate-based compound and, consequently, the effects described above can be maximized.
    [017] In one embodiment, the phosphate-based compound may be at least one material selected from the group consisting of a phosphate-based acrylate represented by Formula 1 below, a polyphosphate-based acrylate

    [018] In Formulas 1 and 2, R1 and R2 are all independently hydrogen, a methyl group, or F, and n is an integer from 1 to 20.
    [019] Specifically, in Formula 1 and/or Formula 2, R1 can be hydrogen and n can be 1.
    [020] The anode can further include a multifunctional compound polymerizable with the phosphate-based compound.
    [021] When the anode active material coating layer is formed together with the polymerizable multifunctional compound with the phosphate-based compound, several characteristics of a battery can be further enhanced.
    [022] That is, when the coating layer of the anode active material is formed by crosslinking polymerization of the phosphate-based compound with high bonding affinity through a structure capable of satisfactorily coordinating lithium ions and the multifunctional composite with excellent elasticity, electrochemical properties and mechanical properties of each material can complement each other.
    [023] In one embodiment, the multifunctional compound may be at least one material selected from the group consisting of a compound based on (meth)acrylic acid ester, a compound based on unsaturated carbonic acid, a compound with vinyl base.
    [024] The (meth)acrylic acid ester-based compound is a (meth)acrylate-based compound having at least two acrylate groups per molecule, and the (meth)acrylate-based compound can be a monomer represented by Formula 3 below or an oligomer thereof.

    [025]In Formula 3, R3, R4, and R5 are all independently hydrogen or a substituted or unsubstituted C1-C4 alkyl group, and m is an integer from 1 to 20.
    [026] In addition, the (meth)acrylic acid ester-based compound can be at least one material selected from the group consisting of diethylene glycol diacrylate (Di(EG)DA), diethylene glycol dimethacrylate (Di(EG) DM), ethylene glycol dimethacrylate (EGDM), dipropylene glycol diacrylate (Di(PG)DA), dipropylene glycol dimethacrylate (Di(PG)DM), ethylene glycol divinyl ether (EGDVE), ethylene triacrylate Ethoxylated trimethylolpropane(6) (ETMPTA), diethylene glycol divinyl ether (Di(EG)DVE), triethylene glycol dimethacrylate (Tri(EG)DM), dipentaerythritol pentaacrylate (DPentA), trimethylolpropane triacrylate (TMPTA ), trimethylolpropane trimethacrylate (TMPTM), propoxylated trimethylolpropane triacrylate(3) (PO(3)TMPTA), propoxylated trimethylolpropane triacrylate(6) (PO(6)TMPTA), poly(ethylene glycol) diacrylate (PA1), and poly(ethylene glycol dimethacrylate), but the embodiments are not limited thereto.
    [027] The multifunctional compound can also form various types of copolymers with the phosphate-based compound, for example, a random copolymer, a block copolymer, a graft copolymer, or the like.
    [028]The amount of the phosphate-based compound can be between 0.01 and 50 parts by weight, in particular between 1 and 30 parts by weight, based on 100 parts by weight of the anode active material.
    [029]The coating layer of the phosphate-based compound may have a thickness of 0.001 μm to 10 μm, in particular 0.1 μm to 5 μm.
    [030]The porosity of the anode can be between 10 and 50%, in particular between 30 and 40%.
    [031] The term "porosity" used herein refers to a ratio of a hollow portion of a porous material to a total volume of the porous material and is also referred to as the degree of pores or void fraction.
    [032] The anode for secondary batteries according to the present invention can be manufactured using a method including: coating an anode slurry including LTO as an anode active material onto a current collector and drying the coated current collector (step (THE)); form a phosphate-based compound coating layer on the surfaces of LTO particles by impregnating the anode manufactured by step (A) with a solution in which the phosphate-based compound is dissolved (step (B) )); and polymerizing the phosphate-based compound by thermal curing, photocuring by irradiation of electron beams or gamma rays, or stabilization reaction at a temperature of 30 °C to 80 °C (step (C)).
    [033] In step (B), the amount of the phosphate-based compound can be from 0.1% by weight to 30% by weight based on a weight of a solvent.
    [034]When the amount of the phosphate-based compound is less than 0.1% by weight based on the weight of the solvent, it is difficult to form the coating layer. On the other hand, when the amount of the phosphate-based compound exceeds 30% by weight based on the solvent weight, a lithium ion transfer rate may decrease and thus battery performance may deteriorate. This is also applied to a case where the multifunctional compound is added to the phosphate-based compound. That is, a total amount (weight) of the phosphate-based compound and the multifunctional compound may be between 0.1 and 30% by weight, in particular between 1 to 20% by weight, based on the weight of the solvent.
    [035] The multifunctional compound polymerizable with the phosphate-based compound can be included in the solution of step (B) in an amount of 0.1% by weight to 10% by weight, in particular 0.1% by weight at 0.5% by weight, based on the weight of the solvent. When the amount of multifunctional compound is too low, its effects are insufficient. On the other hand, when the amount of the multifunctional compound is too large, polymerization with the phosphate-based compound can be difficult to implement.
    [036]The solution in which the phosphate-based compound is dissolved can include a polymerization initiator, an electrolyte solution (plasticizer), and a lithium salt.
    [037]Examples of the polymerization initiator include, but are not limited to, azo-based compounds such as 2,2-azobis(2-cyanobutane), 2,2-azobis(methylbutyronitrile), 2,2'-azoisobutyronitrile (AIBN), and azobisdimethyl-valeronitrile (AMVN), peroxy-based compounds such as benzoyl peroxide, acetyl peroxide, dilauryl peroxide, di-tert-butyl peroxide, cumyl hydroperoxide, and hydrogen peroxide, and hydroperoxides . In particular, the polymerization initiator can be AIBN, 2,2'-azobis(2,4-dimethyl valeronitrile) (V65), di-(4-tertbutylcyclohexyl)-peroxydicarbonate (DBC), or the like.
    [038]The polymerization initiator decomposes at a temperature of 40 °C to 80 °C to form a radical and can react with monomers by free radical polymerization. In general, free radical polymerization is implemented through initiation reaction whereby highly reactive molecules or active sites are temporarily formed, propagation reaction whereby monomers are added to active chain ends and thus active sites are formed again at chain ends, chain transfer reaction whereby active sites are transferred to other molecules, and termination reaction whereby an active chain center is destroyed. Furthermore, polymerization can also be implemented without using a polymerization initiator.
    [039]The electrolyte solution also serves as a plasticizer. For example, the electrolyte solution can be an aprotic organic solvent such as N-methyl-2-pyrrolidinone, propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), dimethyl carbonate (DMC) , diethyl carbonate (DEC), ethyl methyl carbonate (EMC), gamma butyrolactone, 1,2-dimethoxy ethane, tetrahydroxy franc, 2-methyl tetrahydrofuran, dimethylsulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid triester, trimethoxy methane, dioxolane derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives , ether, methyl propionate, or ethyl propionate. The electrolyte solution can be used alone or in combination of at least two of these.
    [040]Lithium salt is a material that is easily soluble in a non-aqueous electrolyte and thus disintegrates into lithium ions. Examples of this include LiCl, LiBr, LiI, LiClO4, LiBF4, LiB10Cl10, LiPF6, LiCF3SO3, LiCF3CO2, LiAsF6, LiSbF6, LiAlCl4, CH3SO3Li, CF3SO3Li, (CF3SO2)2NLi, chloroborate lithium, lower carbonic acid lithium, boaliphatic acid of lithium tetraphenyl, and imide. These lithium salts can be used alone or at least two of these can be used in combination.
    [041] The lithium salt can be included in an amount of 0.01% by weight to 30% by weight, in particular 0.1% by weight to 20% by weight, based on total solids.
    [042] In addition, in order to improve the charge/discharge and flame retardancy characteristics, for example, pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylenediamino, n-glyme, hexaphosphoric triamide, nitrobenzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinone, N,N-substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salts, pyrrole, 2-methoxy ethanol, aluminum trichloride, or the like can be added to the electrolyte. In some cases, in order to communicate incombustibility, the electrolyte may further include a halogen containing solvent such as carbon tetrachloride, ethylene trifluoride, or the like. In addition, in order to improve high temperature storage characteristics, the electrolyte may further include carbon dioxide gas.
    [043] In another embodiment, the anode for secondary batteries according to the present invention can be manufactured using a method including coating an anode slurry including LTO as an anode active material and the phosphate-based compound on a current collector and dry the coated current collector (step (a)) and polymerize the phosphate-based compound by performing thermal curing, photocuring by irradiation of electron beams or gamma rays, or stabilization reaction at a temperature of 30 °C to 80 °C on the anode manufactured in step (a).
    [044] The present invention also provides a secondary battery including the anode for secondary batteries. The secondary battery is manufactured to have a structure in which an electrolyte is included in an electrode assembly including a cathode, an anode, and a separator disposed between the cathode and the anode.
    [045] The cathode for example can be manufactured by coating a mixture of a cathode active material, a conductive material, and a binder on a cathode current collector and drying and pressing the coated current collector. of the cathode. As desired, the mixture can further include a filler.
    [046]The cathode current collector is generally manufactured in a thickness of 3 to 500 µm. The cathode current collector is not particularly limited as long as it does not cause chemical damage to the manufactured lithium secondary battery and has high conductivity. For example, the cathode current collector can be fabricated from stainless steel, aluminum, nickel, titanium, sintered carbon, aluminum, or stainless steel surface treated with carbon, nickel, titanium, or silver, or the like. The cathode current collector may have fine irregularities on a surface of the cathode to increase the adhesion between the cathode active material and the cathode current collector. In addition, the cathode current collector can be used in any of a number of forms including films, foils, foils, meshes, porous structures, foams, and non-woven fabrics.
    [047] Examples of cathode active material include, but are not limited to, layered compounds such as lithium cobalt oxide (LiCoO2) and lithium nickel oxide (Li-NiO2) or compounds substituted with one or more transition metals ; lithium manganese oxides represented by Lii+xMn2-xO4 where 0 < x < 0.33, such as LiMnOa, LiMn2O3, and LiMnO2; lithium copper oxide (Li2CuO2); vanadium oxides such as LiV3O8, LiV3O4, V2O5, and Cu2V2O7; Ni site type lithium nickel oxides having the formula LiNi1-xMxO2 where M = Co, Mn, Al, Cu, Fe, Mg, B, or Ga, and 0.01 < x < 0.3; composite lithium manganese oxides having the formula LiMn2-xMxO2 where M = Co, Ni, Fe, Cr, Zn, or Ta, and 0.01 < x < 0.1 or the formula Li2Mn3MO8 where M = Fe, Co, Ni, Cu, or Zn; LiMn2O4 where some of the Li atoms are replaced with alkaline earth metal ions; disulfide compounds; and Fe2(MoO4)3.
    [048] The conductive material is typically added in an amount of 1 to 50% by weight based on the total weight of the mixture including the cathode active material. There is no particular limit as to the conductive material, as long as it does not cause chemical damage to the manufactured battery and has conductivity. Examples of conductive materials include graphite such as natural or artificial graphite; carbon black such as carbon black, acetylene carbon black, Ketjen black, channel carbon black, furnace carbon black, lamp carbon black, and thermal black; conductive fibers such as carbon fibers and metal fibers; metal powders such as carbon fluoride powder, aluminum powder, and nickel powder; conductive capillary crystals such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; and polyphenylene derivatives.
    [049]The binder is a component that assists in the connection between an active electrode material and the conductive material and in the connection of the active electrode material to an electrode current collector. The binder is typically added in an amount of 1 to 50% by weight based on the total weight of the mixture including the cathode active material. Examples of the binders include polyvinylidene fluoride, polyvinyl alcohols, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ter-polymer of ethylene-propylene-diene (EPDM), sulfonated EPDM, rubber of styrene butadiene, fluorine rubber, and various copolymers.
    [050]The filler is optionally used as a component to inhibit cathode expansion. The filler is not particularly limited as long as it is a fibrous material that does not cause chemical damage to the manufactured battery. Examples of the filler include olefin-based polymers such as polyethylene and polypropylene; and fibrous materials such as fiberglass and carbon fiber.
    [051]The anode can be manufactured by coating an anode active material over an anode current collector and drying the anode coated current collector. In some cases, the components described above can still be coated onto the anode current collector.
    [052]The anode current collector is typically manufactured in a thickness of 3 to 500 µm. The anode current collector is not particularly limited as long as it does not cause chemical damage to the manufactured secondary battery and has conductivity. For example, the anode current collector can be fabricated from copper, stainless steel, aluminum, nickel, titanium, sintered carbon, copper, or stainless steel surface treated with carbon, nickel, titanium, or silver, and aluminum-cadmium alloys. . Similar to the cathode current collector, the anode current collector can also have fine irregularities on a surface thereof to enhance the adhesion between the anode current collector and the anode active material and be used in various forms including films, sheets , metallic sheets, nets, porous structure, foams, and non-woven cloths.
    [053]The active anode material can be LTO as described above.
    [054]In particular, the LTO can be Li4Ti5O12, LiTi2O4, or a mixture of these and, more particularly, it can be Li4Ti5O12.
    [055] In addition, examples of the anode active material include carbon such as hard carbon and graphite-based carbon; composite metal oxides such as LixFe2O3 where 0 < x < 1, LixWO2 where 0 < x < 1, SnxMei-xMe’yOz where Me: Mn, Fe, Pb, or Ge; Me’: Al, B, P, Si, Group I, II and III elements, or halogens; 0 < x < 1; 1 < y < 3; and 1 < z < 8; lithium metals; lithium alloys; silicon-based alloys; tin-based alloys; metal oxides such as SnO, SnO2, PbO, PbO2, Pb2O3, Pb3O4, Sb2O3, Sb2O4, Sb2O5, GeO, GeO2, Bi2O3, Bi2O4, and Bi2O5; conductive polymers such as polyacetylene; and Li-Co-Ni based materials, and these anode active materials can be used in combination.
    [056] The secondary battery according to the present invention may be a lithium secondary battery, and examples thereof include, but are not limited to, a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, and a lithium ion polymer secondary battery. The secondary battery can be manufactured in various forms. For example, an electrode assembly can be manufactured in various shapes including a roquette type, a battery type, a battery/hinge type, and the like, and the secondary battery can have a structure in which an electrode assembly is accommodated in a battery case such as a cylindrical can, a rectangular can, or a laminated sheet including a metallic layer and a resin layer. Such a configuration is well known in the art and thus a detailed description of it will be omitted here.
    [057]The secondary battery can be used as a power supply for small electronic devices and medium and large scale devices as described below.
    [058] The present invention also provides a battery module including the secondary battery as a unit battery and a battery pack including the battery module.
    [059]The battery pack can be used as a power supply for medium and large scale devices that require high temperature stability, long cycle life expectancy, and high rate characteristics.
    [060]Examples of medium and large scale devices include, but are not limited to, electric motor powered power tools; electric vehicles (EVs), hybrid electric vehicles (HEVs), and plug-in hybrid electric vehicles (PHEVs); two-wheeled electric vehicles such as electric bicycles and electric scooters; electric golf carts; and systems for storing power. Effects of the Invention
    [061] As evident from the foregoing, an anode for secondary batteries according to the present invention uses, as an anode active material, lithium-titanium oxide, a surface of which is coated with a phosphate-based compound. In fact, and thus, it can exhibit excellent high temperature storage, high energy production characteristics, and excellent life expectancy characteristics due to a stabilized electrode interface. Brief Description of Drawings
    [062] The above and other objectives, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in combination with the attached drawing, in which:
    [063] FIG. 1 is a graph showing cycle characteristics measured in a chamber at 45 °C according to Experimental Example 2. Best Mode
    [064]Now, the present invention will be described in more detail with reference to the following examples. These examples are provided for illustration of the present invention only and are not to be construed as limiting the scope and spirit of the present invention. <Example 1> Anode Fabrication
    [065]Li1,33Ti1,67O4 as an anode active material, Denka black as a conductive material, and PVdF as a binder were added to NMP and mixed into it at a weight ratio of 95:2.5:2, 5 to prepare an anode mix. Subsequently, the anode mixture was coated at a thickness of 200 µm onto a Cu sheet having a thickness of 20 µm and rolled and dried, thereby completing the fabrication of an anode.
    [066] The fabricated anode was impregnated into a coating solution prepared by dissolving phosphate-based acrylate represented by the Formula below as a phosphate-based material in DMC as a solvent in an amount of 10% in weight based on a weight of solvent for 30 minutes to form a coating layer over it, and the resulting mixture was irradiated with electron beams to obtain an anode provided over it with the coating layer formed from the compound with phosphate base.
    Battery Manufacturing
    [067]LiNi0.5Mn1.5O4 as a cathode active material, Denka black as a conductive material, and PVdF as a binder were added to NMP and mixed into it at a weight ratio of 95:2.5: 2.5 to prepare a cathode mixture, and the cathode mixture was coated onto an Al sheet having a thickness of 20 µm and rolled and dried, thereby completing the fabrication of a cathode.
    [068]Subsequently, a polyethylene film (Celgard®, thickness: 20 μm) as a separator was interposed between the fabricated anode and cathode, and a liquid electrolyte containing 1M LiPF6 dissolved in EC/EMC (=1/2 ( % in vol)) was injected into this, thereby completing the fabrication of a bag-type battery. <Example 2>
    [069]A pouch battery was manufactured in the same manner as in example 1, except that the Formula 2 polyphosphate based acrylate where R1 is H and n is 1 was used as a phosphate based material. <Example 3>
    [070] A pouch battery was manufactured in the same manner as in example 1, except that dipentaerythritol pentaacrylate (DPentA) as a multifunctional compound was further added to the solution containing the phosphate-based material in an amount of 0.2 % by weight based on weight of solvent. <Example 4>
    [071] A pouch battery was manufactured in the same manner as in example 2, except that DPentA as a multifunctional compound was further added to the solution containing the phosphate-based material in an amount of 0.2 wt% based on weight of the solvent. <Example 5> Anode Fabrication
    [072]Li1,33Ti1,67O4 as an anode active material, Denka black as a conductive material, and PVdF as a binder were added to NMP and mixed into it at a weight ratio of 95:2.5:2, 5 to prepare an anode mix. Subsequently, the anode mixture was coated at a thickness of 200 µm onto a Cu sheet having a thickness of 20 µm and rolled and dried, thereby completing the fabrication of an anode.
    [073] The fabricated anode was impregnated into a coating solution prepared by dissolving phosphate-based acrylate represented by Formula a below as a phosphate-based material in DMC as a solvent in an amount of 0.2 % by weight based on a weight of solvent for 30 minutes to form a coating layer over it, and the resulting mixture was irradiated with electron beams to obtain an anode provided over it with the coating layer formed from the phosphate-based compound.
    Battery Manufacturing
    [074]LiNi0.5Mn1.5O4 as a cathode active material, Denka black as a conductive material, and PVdF as a binder were added to NMP and mixed into it at a weight ratio of 95:2.5: 2.5 to prepare a cathode mixture, and the cathode mixture was coated onto a sheet of Al having a thickness of 20 µm and rolled and dried, thereby completing the fabrication of a cathode.
    [075]Subsequently, a polyethylene film (Celgard®, thickness: 20 μm) as a separator was interposed between the fabricated anode and cathode, and a liquid electrolyte containing 1M LiPF6 dissolved in EC/EMC (=1/2 ( % in vol)) was injected into this, thereby completing the fabrication of a bag-type battery. <Example 6>
    [076] A pouch battery was manufactured in the same manner as in example 5, except that DPentA as a multifunctional compound was further added to the solution containing the phosphate-based material in an amount of 0.2 wt% based on weight of the solvent. <Comparative Example 1>
    [077]A bag-type battery was manufactured in the same manner as in example 1, except that the phosphate-based acrylate was not added to the fabricated anode. <Comparative Example 2>
    [078] A 2016 coin cell was manufactured in the same manner as in example 1, except that a coating solution, prepared by adding the compound of Formula a to the solvent in an amount of 40% by weight based on the weight of the solvent , it was used. <Experimental Example 1>
    [079] Batteries (design capacity: 10.2 mAh) manufactured in accordance with Examples 1 to 6 and Comparative Examples 1 and 2 were subjected to formation at 2.75 V, and charge/discharge cycles of C rate of each battery were performed at a voltage of 2.75 V to 1.6 V and the discharge capacity of these was confirmed. The results are shown in Table 1 below. [Table 1]

    <Experimental Example 2>
    [080]The 5C/5C cycle characteristics of the batteries of Examples 1 and 3 and Comparative Examples 1 and 2 were measured during charging and discharging in a chamber at 45 °C at a voltage of 1.6 V at 2, 75V and 5C. Measurement results are shown in FIG. 1.
    [081] Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the claims attached.
    权利要求:
    Claims (14)
    [0001]
    1. Anode for secondary batteries CHARACTERIZED by the fact that it comprises an anode mixture comprising an anode active material, coated onto a current collector, wherein the anode active material comprises lithium-titanium oxide (LTO) particles provided on the surfaces thereof with a crosslinked polymer coating layer, wherein the LTO particles with the crosslinked polymer coating layer formed thereon retain a porous structure formed therebetween, and a crosslinked polymer of the coating layer is a composite based on phosphate, and wherein the phosphate-based compound is at least one material selected from the group consisting of a phosphate-based acrylate represented by Formula 1 below, a pyrophosphate-based acrylate represented by Formula 2 below, and a phosphate-based urethane acrylate:
    [0002]
    2. Anode, according to claim 1, CHARACTERIZED by the fact that it further comprises a polymerizable multifunctional compound with the phosphate-based compound.
    [0003]
    3. Anode according to claim 2, CHARACTERIZED by the fact that the multifunctional compound is at least one material selected from the group consisting of a compound based on (meth)acrylic acid ester, an acid based compound unsaturated carbon dioxide, and a vinyl-based compound.
    [0004]
    4. Anode according to claim 3, CHARACTERIZED by the fact that the compound based on (meth)acrylic acid ester is a compound based on (meth)acrylate having at least two acrylate groups per molecule.
    [0005]
    5. Anode, according to claim 4, CHARACTERIZED by the fact that the compound based on (meth)acrylate is a monomer represented by Formula 3 below or an oligomer thereof:
    [0006]
    6. Anode according to claim 4, CHARACTERIZED by the fact that the (meth)acrylic acid ester-based compound is at least one material selected from the group consisting of diethylene glycol diacrylate (Di(EG)DA), diethylene glycol dimethacrylate (Di(EG)DM), ethylene glycol dimethacrylate (EGDM), dipropylene diacrylate (Di(PG)DA), dipropylene glycol dimethacrylate (Di(PG)DM), divinyl ether of ethylene glycol (EGDVE), ethoxylated trimethylolpropane triacrylate(6) (ETMPTA), diethylene glycol divinyl ether (Di(EG)DVE), triethylene glycol dimethacrylate (Tri(EG)DM), dipentaerythritol pentaacrylate (DPentA), triacrylate of trimethylolpropane (TMPTA), trimethylolpropane trimethacrylate (TMPTM), propoxylated trimethylolpropane triacrylate(3) (PO(3)TMPTA), propoxylated trimethylolpropane triacrylate(6) (PO(6)TMPTA), diacrylate of poly(ethylene glycol) (PA1), and poly(ethylene glycol) dimethacrylate.
    [0007]
    7. Anode according to claim 1, CHARACTERIZED by the fact that the amount of the phosphate-based compound is 0.01 part by weight per 50 parts by weight based on 100 parts by weight of the active anode material.
    [0008]
    8. Anode according to claim 1, CHARACTERIZED by the fact that the crosslinked polymer coating layer formed from the phosphate-based compound has a thickness of 0.001 μm to 10 μm.
    [0009]
    9. Anode, according to claim 1, CHARACTERIZED by the fact that it has a porosity of 10% to 50%.
    [0010]
    10. Method of manufacturing the anode for secondary batteries, as defined in claim 1, CHARACTERIZED by the fact that it comprises: coating an anode slurry comprising lithium-titanium oxide (LTO) as an active anode material and the compound based on phosphate over a current collector and dry the coated current collector; and polymerize the phosphate-based compound through thermal curing, photocuring by irradiation of electron beams or gamma rays, or stabilization reaction at a temperature of 30°C to 80°C at the anode manufactured by the coating.
    [0011]
    11. Secondary battery CHARACTERIZED by the fact that it comprises the anode for secondary batteries as defined in any one of claims 1 to 9.
    [0012]
    12. Secondary battery, according to claim 11, CHARACTERIZED by the fact that it is a lithium secondary battery.
    [0013]
    13. Battery module CHARACTERIZED by the fact that it comprises the secondary battery, as defined in claim 12, as a battery unit.
    [0014]
    14. Battery pack CHARACTERIZED by the fact that it comprises the battery module as defined in claim 13.
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    同族专利:
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    EP2874207A4|2016-01-20|
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    EP2874207B1|2017-12-20|
    JP6203834B2|2017-09-27|
    KR101558864B1|2015-10-12|
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    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2019-10-01| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-02-17| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-05-25| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-07-13| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 10/07/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    KR20120075122|2012-07-10|
    KR10-2012-0075122|2012-07-10|
    PCT/KR2013/006122|WO2014010930A1|2012-07-10|2013-07-10|Negative electrode for secondary battery, and secondary battery comprising same|
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