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    • 专利摘要:
    SECONDARY BATTERY INCLUDING ELECTROLYTE ADDITIVE. The present invention describes a secondary battery including a set of electrodes, which includes a cathode, an anode and a separator interposed between them, and an electrolyte, wherein the anode includes a lithium titanium oxide (LTO) as an active material anode, and the electrolyte contains a phosphate-based compound as an additive.
    公开号:BR112014030392B1
    申请号:R112014030392-4
    申请日:2013-07-10
    公开日:2021-06-08
    发明作者:Kyoung-Ho Ahn；Doo-Kyung Yang；Jong-Ho Jeon；Yoo-Seok Kim；Jung-Hoon Lee；Chul- Haeng Lee；Min-Jung Kim；Yi-Jin Jung
    申请人:Lg Chem, Ltd；
    IPC主号:
    专利说明:

    TECHNICAL FIELD
    [001] The present invention relates to a secondary battery that includes a set of electrodes comprising a cathode, an anode and a separator interposed between them, and an electrolyte, in which the anode includes lithium and titanium oxide (LTO), as an anode active material, and the electrolyte contains a phosphate-based compound as an additive. BACKGROUND
    [002] Technological development and increased demand for mobile devices have caused a rapid increase in demand for secondary batteries, as energy sources. Among these secondary batteries, lithium secondary batteries, having a high energy density, a high operating voltage, a long service life and a low self-discharge regime, are commercially available and widely used.
    [003] In addition, a greater interest in environmental aspects has recently sparked a major research effort, associated with electric vehicles (EV) and hybrid electric vehicles (HEV), as alternatives to vehicles that use fossil fuels, such as electric vehicles. gasoline and diesel vehicles, which are major causes of air pollution. These electric vehicles generally use secondary nickel-metal hydride (Ni-MH) batteries as energy sources. However, a large study effort, associated with the use of secondary lithium batteries, having a high energy density, a high discharge voltage and a stable output, is currently being made and some are commercially available.
    [004] Lithium secondary batteries can be classified as lithium ion batteries containing liquid electrolytes per se, lithium ionic batteries and polymerPetition 870190132678, of 12/12/2019, p. 9/34 2/21containing liquid electrolytes in a gel form, and lithium polymer batteries containing solid electrolytes, depending on the type of electrolyte used. Particularly, the use of ionic lithium and polymer batteries or polymer gel batteries is increasing, due to several of their advantages, such as greater safety due to the low probability of fluid leakage, compared to liquid electrolyte batteries, and the possibility of obtaining very thin and light batteries.
    [005] An ionic lithium battery is manufactured by impregnating a liquid electrolyte containing a lithium salt in a set of electrodes, which includes a cathode and an anode, each of which is formed by applying an active material to a collector of current, with a porous separator interposed between the cathode and the anode.
    [006] The processes for manufacturing a polymer and ionic lithium battery are divided into a manufacturing process for a non-crosslinked polymer battery and a manufacturing process for a directly crosslinked polymer battery, depending on the type of a matrix material for electrolyte impregnation. Acrylate and methacrylate-based materials, having a high radical polymerization reactivity, and ether-based materials, having a high electrical conductivity, are typically used as the polymeric matrix materials. In particular, in the manufacture of directly crosslinked polymer batteries, a battery is manufactured by: placing a gelatinous roll type or a battery-type electrode assembly, composed of electrode plates and a porous separator in a pouch; injecting a thermally polymerizable poly(ethylene oxide) (PEO) based monomer or oligomer crosslinking agent and an electrolyte composition into the pouch; and thermally cure the injected materials. Manufacturing batteries in this way is advantageous in that the plates and separate electrodes of conventional lithium ion batteries are used without Petition 870190132678, 12/12/2019, p. 10/34 3/21 changes. However, directly crosslinked polymer battery manufacture presents problems in that a crosslinking agent is not fully cured and remains in the electrolyte, which increases viscosity. This makes uniform impregnation difficult, thereby greatly degrading the properties of the batteries.
    [007] A carbon-based material is typically used as an anode active material for secondary lithium batteries. However, the carbon-based material has a low potential of 0V, relative to lithium, and thus reduces the electrolyte, with the generation of gases. Lithium titanium oxide (LTO), having a relatively high potential, is also used as an anode active material for lithium secondary batteries to solve these problems.
    [008] However, when LTO is used as an anode active material, LTO acts as a catalyst, generating a large amount of hydrogen gas during the activation and charge/discharge processes, which causes a reduction in the safety of the secondary batteries.
    [009] Thus, there is a great need to provide a technology that ensures battery safety by solving the problems mentioned above, while maintaining the overall performance of the batteries. DESCRIPTION TECHNICAL PROBLEM
    [010] Therefore, the present invention was developed to solve the technical problems mentioned above and others that still need to be solved.
    [011] As a result of intensive studies and various experiments, it was found in the present invention that desired effects are obtained when a secondary battery, including lithium titanium oxide (LTO), as an anode active material, and a compound to Phosphate base, as an electrolyte additive, is used. The present invention was completely based on this discovery. Petition 870190132678, dated 12/12/2019, p. 11/34 4/21 TECHNICAL SOLUTION
    [012] According to the present invention, the objects mentioned above and others can be achieved by provision of a secondary battery, including a set of electrodes, comprising a cathode, an anode and a separator interposed between them, and an electrolyte, in that the anode includes lithium titanium oxide (LTO) as an active material, and the electrolyte contains a phosphate-based compound as an additive.
    [013] In a specific embodiment, the electrolyte can be, but is not limited to, any of a liquid electrolyte, a gel electrolyte and a solid electrolyte. Specifically, the electrolyte can be a liquid electrolyte or a polymer gel electrolyte.
    [014] When the electrolyte is a liquid electrolyte, the decomposition of the electrolyte can be promoted by a parallel reaction of the electrolyte with the active material, thereby generating gas as described above. This gas can cause secondary battery safety problems such as expansion or explosion. Thus, the secondary battery, according to the present invention, uses a liquid electrolyte with a phosphate-based compound added to it, to solve these problems.
    [015] When the electrolyte is a polymer gel electrolyte, the phosphate-based compound additive, which reacts as a crosslinking agent, is added to the polymer gel electrolyte. This provides higher cycle characteristic effects, while achieving stabilization of the electrode interfaces, thereby greatly inhibiting the expansion caused by gas generation during storage at a high temperature. Therefore, the effects of greatly improved battery life and safety are also achieved.
    [016] In this case, it is believed that, since the compound based on Petition 870190132678, of 12/12/2019, p. 12/34 5/21phosphate has a high reactivity with radicals, increases the degree of polymerization reaction, thereby improving the electrochemical stability of the final electrolyte. In addition, LTO, used as an active material, acts as a catalyst to promote crosslinking polymerization of the phosphate-based compound, thereby maximizing the effects described above.
    [017] Particularly, when the electrolyte is a polymer gel electrolyte, the parallel reactions of the electrolyte with the electrodes are reduced, during repeated charges/discharges, since an area of the electrolyte, in contact with the electrodes, is reduced and swelling is also inhibited, due to a reduction in vapor pressure, since the electrolyte is in a polymer gel form.
    [018] In one embodiment, the phosphate-based compound may include at least one selected from the group consisting of a phosphate-based acrylate of formula (I), a pyrophosphate-based acrylate of formula (2), and a urethane-based acrylate of phosphate:

    [019] where R1 and R2 are both independently hydrogen, methyl or F, and n is an integer from 1 to 20.
    [020] The electrolyte may also contain a multifunctional compound, polymerizable with the phosphate-based compound.
    [021] When a multifunctional compound, polymerizable with the phosphate-based compound, is additionally used as an electrolyte additive, the compound Petition 870190132678, 12/12/2019, p. 13/34 6/21 multifunctional and the phosphate-based compound can complement each other's electrochemical and mechanical characteristics, thereby further improving the overall characteristics of the battery.
    [022] Particularly, when a polymer gel electrolyte is prepared by using both phosphate-based compounds and a polymerizable multifunctional compound with the phosphate-based compound, physical properties with greater elasticity are obtained. That is, a phosphate-based compound, which has a structure that provides easier coordination with lithium ions, thus, presenting a greater bond strength, and a multifunctional compound, having high elasticity, are polymerized by joint crosslinking , so that the phosphate-based compound and the multifunctional compound complement each other's electrochemical and mechanical characteristics.
    [023] In one embodiment, the multifunctional compound may include at least one selected from the group consisting of a (meth)acrylic acid ester compound, an unsaturated carbonic acid compound, and a vinyl compound.
    [024] The (meth)acrylic acid ester compound may include a (meth)acrylate compound having at least two acrylate groups per molecule, and the (meth)acrylate compound may include a formula (3) or monomer an oligomer of it:

    [025] where R3, R4 and R5 are all independently hydrogen or C1 - C4 - substituted or unsubstituted alkyl, and m is an integer from 1 to 20.
    [026] In addition, the (meth)acrylic acid ester compound may include, but is not limited to, at least one 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), ethylene glycol divinyl ether Petition 870190132678, 12/12/2019, p. 14/34 7/21(EGDVE), ethoxylated trimethylolpropane triacrylate (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), polyethylene glycol diacrylate (PA1 ) and polyethylene glycol dimethacrylate.
    [027] The multifunctional compound, together with the phosphate-based compound, can form various types of copolymers, for example, random copolymers, block copolymers and graft copolymers.
    [028] The electrolyte may contain 0.1 to 1%, more specifically, 0.1 to 0.5% by weight of the multifunctional compound, polymerizable with the phosphate-based compound, based on the total weight of the electrolyte.
    [029] The electrolyte may contain 0.01 to 30%, more specifically, 0.01 to 20% by weight of the phosphate-based compound, based on the total weight of the electrolyte.
    [030] If the content of the phosphate-based compound is excessively low, when the electrolyte is a liquid electrolyte, the effects of an improved safety are not fully achieved. Conversely, if the content of the phosphate-based compound is excessively high, the overall characteristics of the batteries can be degraded, as the lithium salt content is relatively low, although safety is improved.
    [031] If the content of the phosphate-based compound is excessively low, when the electrolyte is a polymer gel electrolyte, the gel polymers are not easily formed, since the phenomenon of battery swelling, which occurs when a liquid electrolyte is used, it can get worse, and the formation of a substrate, having a desired thickness, can be difficult. Conversely, if the content of the phosphate-based compound is excessively high, the density of the gel polymers is increased and the lithium ionic conduction (or conductivity) regime is Petition 870190132678, 12/12/2019, p. 15/34 8/21 consequently reduced, causing lithium precipitation, with the consequence that the battery performance is deteriorated. Furthermore, the viscosity is increased so that it may be difficult to apply the electrolyte uniformly to a corresponding part.
    [032] The same is true when the multifunctional compound is added to the phosphate-based compound. Thereby, the electrolyte can contain the phosphate-based compound and the multifunctional compound in a total proportion of 0.01 to 30%, more specifically 0.1 to 5% by weight of the total weight of the electrolyte.
    [033] The liquid electrolyte may include an electrolyte (plasticizer) and a lithium salt. When the electrolyte is a polymer gel electrolyte, the electrolyte may further include a polymerization initiator.
    [034] The electrolyte also serves as a plasticizer. Examples of the electrolyte include aprotic organic solvents such as N-methyl-pyrrolidinone, propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC ), methyl ethyl carbonate (EMC), gamma-butyrolactone, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyl tetrahydrofuran, dimethylsulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate , methyl acetate, phosphoric acid triester, trimethoxy methane, dioxolone derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-1-imidazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, ether, methyl propionate and propionate ethyl. These materials can be used separately as a mixture of two or more of them.
    [035] Lithium salt is a material that dissolves and dissociates into lithium ions in the non-aqueous electrolyte. Examples of the lithium salt include LiCl, LiBr, LiI, LiClO4, LiBF4, LiB10Cl10, LiPF6, LiCF3SO3, LiCF3CO2, LiAsF6, LiSbF6, LiAlCl4, CH3SO3Li, CF3SO3Li, (CF3SO2)2NLi, lithium chloroborane, lithium carboxylic acid salt lower, lithium tetraphenylborate and lithium imides. These materials can Petition 870190132678, of 12/12/2019, p. 16/34 9/21 be used alone or in a mixture of two or more of them.
    [036] The electrolyte may contain 0.01 to 30%, more specifically 0.1 to 20% by weight of the lithium salt, based on the total weight of the solid components included in the electrolyte.
    [037] Examples of the polymerization initiator may include azo compounds such as 2,2-azobis (2-cyanobutane), 2,2-azobis (methylbutyronitrile), 2,2'-azoisobutyronitrile (AIBN) and azobisdimethyl-valeronitrile (AMVN), peroxy compounds such as benzoyl peroxide, acetyl peroxide, dilauryl peroxide, di-tert-butyl peroxide, cumyl peroxide and hydrogen peroxide, and hydroperoxides. Specifically, AIBN, 2,2'-azobis (2,4-dimethylvaleronitrile) (V65), di-(4-tert-butylcyclohexyl)-peroxydicarbonate (DBC) or the like can be used as the polymerization initiator.
    [038] The polymerization initiator can decompose at a temperature of 40 to 80°C, to form radicals, and can react with the monomers through polymerization via free radicals, to form a polymer gel electrolyte. Generally, polymerization via free radicals is conducted by sequential reactions, including an initiation reaction involving the formation of transient molecules having high reactivity or active sites, a propagation reaction involving the reformation of active sites at the ends of chains by adding monomers to the active chain ends, a chain transfer reaction involving the transfer of active sites to other molecules, and a termination reaction involving the destruction of active chain centers. Of course, polymerization can also be carried out without a polymerization initiator.
    [039] Furthermore, to improve the charge/discharge characteristics and flame retardancy, for example, pyridine, triethyl phosphite, triethanolamine, cyclic ether, ethylenediamine, n-glyme, hexaphosphoric triamide, nitrobenzene derivatives, sulfur, dyes of quinone imines, N-substituted oxazolidinone, imidazoline Petition 870190132678, 12/12/2019, p. 17/34 10/21N,N-substituted, ethylene glycol dialkyl ether, ammonium salts, pyrroles, 2-methoxy ethanol, aluminum trichloride or the like can be added to the electrolyte. Where appropriate, the non-aqueous electrolyte may further include a halogen containing solvent, such as carbon tetrachloride or ethylene trifluoride, to impart incombustibility. Furthermore, the non-aqueous electrolyte can additionally include carbon dioxide gas to improve the high temperature storage characteristics.
    [040] The secondary battery according to the present invention may be a lithium ion battery. The lithium ion battery can be manufactured by: mounting a set of electrodes in a battery housing; injection of a mixture of a phosphate-based compound, an electrolyte and a lithium salt into the battery case, followed by sealing; and performing a formation process to activate the battery, and an aging process to stabilize the activated battery.
    [041] However, when the electrolyte is a polymer-in-gel electrolyte, an activation process is conducted after the gel reaction. When the phosphate-based compound is used as an additive to the electrolyte, a process, in which film formation is induced by wetting and charge/discharge, can be employed while the gel reaction is omitted. In a basic process, the battery is charged to a level at which an electrochemical decomposition reaction of monomers can take place, and degassing is then carried out.
    [042] The formation process is a process that activates the battery by repeating the charge/discharge cycles. The aging process is a process that stabilizes the battery, activated in the formation process, by allowing the battery to stand for a certain period of time.
    [043] The conditions under which the formation process and the aging process are conducted are not particularly limited and are adjustable within conventional ranges well known in the art. Petition 870190132678, 12/12/2019, p. 18/34 11/21
    [044] In a specific embodiment, the mixture is injected into the battery casing (primary injection), and the battery structure is left standing for a certain period of time (eg 10 hours), so that the impregnation uniform mixture in the battery casing is achieved. The battery is then charged for activation. In the charge-to-activation process, the gases generated during the formation of a protective film for the anode are removed. Afterwards, the battery is again left standing for a certain period of time (eg 12 hours) and charged for activation, thereby completing the manufacture of the battery.
    [045] The secondary battery according to the present invention can be a lithium ionic polymer battery. Specifically, the lithium ion polymer battery can be manufactured using a process including: (a) mounting an electrode array in a battery housing; (b) injecting a mixture of a phosphate-based compound, a polymerization initiator, an electrolyte and a lithium salt into the battery housing, followed by sealing; and (c) polymerizing the phosphate-based compound to form a polymer gel electrolyte. Specifically, step (c) may include: (c1) subjecting the battery to thermal curing, photocuring by means of irradiation with electronic beams or gamma rays, or a stabilization reaction at 30 - 80°C, to polymerize the compound phosphate-based; and (c2) conduct a formation process to activate the battery and an aging process to stabilize the activated battery.
    [046] Specifically, the crosslinking reaction can be conducted under inert conditions. Since the reaction of radicals with atmospheric oxygen, serving as a radical scavenger, is fundamentally blocked under an inert atmosphere, it is possible to accentuate the degree of reaction to a level at which substantially no unreacted monomer is present. This prevents degradation in charge/discharge performance caused by a higher content of unreacted monomers remaining within the battery. Petition 870190132678, 12/12/2019, p. 19/34 12/21
    [047] Inert atmosphere conditions are not particularly limited. Known gases with low reactivity can be used. For example, at least one selected from the group consisting of nitrogen, argon, helium and xenon can be used as the inert gases.
    [048] Phosphate-based compounds are combined by means of cross-linking polymerization reaction, to form cross-linked polymers having a three-dimensional network structure, and the polymers are then uniformly impregnated with the electrolyte.
    [049] The crosslinked polymer electrolyte is electrochemically stable and therefore can be stably present in the battery without being damaged even after repeated charge/discharge cycles. Therefore, it is possible to improve the safety of the battery and obtain excellent mechanical properties, such as elongation and bending properties. Further, battery performance deterioration can be minimized due to the continuous migration and transfer of lithium ions by the polymer-in-polar gel electrolyte.
    [050] The formation and aging processes are conducted in the same way as described above. During the forming process, lithium ions, which are released from lithium and metal oxide, used as the cathode, by charging the battery, migrate and intercalate into the carbon electrode, used as the anode. In this case, compounds such as Li2CO3, LiO and LiOH, which are produced by reacting highly reactive lithium with the carbon anode, form a solid electrolyte interface (SEI) film on the anode surface. In that case, an unreacted crosslinking agent may undergo further reaction.
    [051] In a specific embodiment, the mixture is injected into the battery casing (primary injection), and the battery structure is left standing for a certain period of time (eg 3 hours), so that the impregnation uniform mixture in the battery case is obtained. Thermal polymerization is then Petition 870190132678, of 12/12/2019, p. 20/34 13/21 conducted under the conditions specified above. The battery is then charged for activation. In the charge-to-activation process, the gases generated during the formation of a protective film for the anode are removed, and a certain amount of supplemental mixture is secondarily injected into the battery housing. Afterwards, the battery is again left standing for a certain period of time (eg 12 hours) and charged for activation, thus completing the manufacture of the battery.
    [052] The secondary battery is generally manufactured by incorporating an electrolyte into an array of electrodes, including a cathode and anode with a separator interposed between them.
    [053] The cathode is prepared, for example, by applying a mixture of a cathode active material, a conductive material and a binder to a cathode current collector, followed by drying and compression. A filler can be added to the mix if necessary.
    [054] The cathode current collector is generally manufactured at a thickness of 3 to 500 µm. Any cathode current collector can be used without particular limitation, as long as a high conductivity is provided, without causing chemical variations in the battery. Examples of the cathode current collector include stainless steel, aluminum, nickel, titanium, sintered carbon, or aluminum or stainless steel surface treated with carbon, nickel, titanium, or silver. The cathode current collector can include fine irregularities in its surface so as to accentuate the adhesion of the active cathode material. Furthermore, the cathode current collector can be used in various forms such as a film, a sheet, a net, a film, a porous structure, a foam and a non-woven cloth.
    [055] Examples of cathode active material include, but are not limited to: stratified compounds such as lithium cobalt oxide (LiCoO2) and Petition 870190132678, 12/12/2019, p. 21/34 14/21 lithium nickel oxide (LiNiO2), alone or substituted by one or more transition metals; lithium manganese oxides such as Lii+xMn2-xO4 (where 0 < x < 0.33), LiMnO3 and LiMnO2; lithium copper oxide (Li2CuO2); vanadium oxides such as LiV3O8, LiFe3O4, V2O5 and Cu2V2O7; lithium and nitrogen oxides of the nickel site type represented by LINHI-XMXO2 (M = Co, Mn, Al, Cu, Fe, Mg, B or Ga and 0.01 < x < 0.3; composite oxides of lithium and manganese represented by LiMn2-xMxO2 (M = Co, Ni, Fe, Cr, Zn or Ta and 0.01 < x < 0.1) or Li2Mn3MO8 (M = Fe, Co, Ni, Cu or Zn); LiMn2O4, in that Li is partially replaced by alkaline earth metal ions; compounds of disulfides; and Fe2(MoO4)3.
    [056] Conductive material is commonly added at a content of 0.01 to 50% by weight, based on the total weight of the mixture, including the active cathode material. Any conductive material can be used without particular limitation, as long as adequate conductivity is provided, without causing chemical variations in the battery. Examples of the conductive material include graphite such as natural or artificial graphite, carbon blacks such as acetylene black, Ketjen black, channel black, furnace black, lamp black and thermal black, conductive fibers such as fibers of carbon and metal fibers, metal powders such as carbon fluoride, aluminum and nickel powders, conductive monocrystalline wires such as zinc oxide and potassium titanate monocrystalline wires, conductive metal oxides such as titanium oxide, and polyphenylene derivatives .
    [057] The binder is a component that assists in binding an active material to a conductive material and a current collector. Binder is commonly added at a content of 1 to 50% by weight, based on the total weight of the compound including the cathode active material. Examples of the binder include poly(vinylidene fluoride), poly(vinyl alcohol), carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymers (EPDM), EPMSPetition 870190132678, of 12/12/2019, p. 22/34 15/21 Sulphonates, styrene-butadiene rubbers, fluorinated rubbers and various copolymers.
    [058] Charge is a component optionally used to inhibit cathode expansion. Any charge can be used without particular limitation, as long as the charge is a fibrous material, which does not cause chemical variations in the battery. Examples of filler include olefin-based polymers such as polyethylene and polypropylene, and fibrous materials such as glass fibers and carbon fibers.
    [059] For example, the anode is prepared by applying an anode active material to an anode current collector, followed by drying and compression. The anode can include further components if necessary, as described above.
    [060] The anode current collector is generally manufactured at a thickness of 3 to 500 µm. Any anode current collector can be used without particular limitation, as long as adequate conductivity is provided without causing chemical variations in the battery. Examples of the anode current collector include copper, stainless steel, aluminum, nickel, titanium, sintered carbon, copper, or stainless steel surface treated with carbon, nitrogen, titanium or silver, or an aluminum-cadmium alloy. Similar to the cathode current collector, the anode current collector can include fine irregularities in its surface so as to accentuate the bond strength to the anode active material. Furthermore, the anode current collector can be provided in various forms, such as a film, a sheet, a film, a net, a porous structure, a foam and a non-woven cloth.
    [061] Lithium titanium oxide can be used as the anode active material as described above.
    [062] Specifically, lithium titanium oxide can be Li4Ti5O12, LiTi2O4 or a mixture of them. More specifically, lithium titanium oxide can be Li4Ti5O12.
    [063] Examples of anode active material may include a mixture of Petition 870190132678, dated 12/12/2019, p. 23/34 16/21 carbon, such as graphitized carbon or not, a metallic composite oxide such as LixF2O3 (0 < x < 1), LixWO2 (0 < x < 1) or SnxMei-xMe'yOz (Me: Mn, Fe, Pb or Ge; Me': Al, B, P, Si, elements from groups I, II and III of the periodic table, or halogens; 0 < x < 1, 1 < y < 3 and 1 < z < 8), lithium metallic, a lithium alloy, a silicon-based alloy, a tin-based alloy, metal oxide such as SnO, SnO2, PbO, PbO2, Pb2O3, Pb3O4, Sb2O3, Sb2O4, Sb2O5, GeO, GeO2, Bi2O3, Bi2O4 or Bi2O5, a conductive polymer such as polyacetylene, and a Li - Co - Ni based material.
    [064] The secondary battery according to the present invention can be manufactured in various forms. For example, the electrode array can be constructed in a gelatinous roll frame, a stacked frame, a stacked/folded frame, or the like. The battery can be structured such that an electrode array is installed within a battery housing, made of a cylindrical can, a prismatic can, or a laminated sheet, including a metallic layer and a resin layer. This battery structure is widely known in the art and therefore a detailed description of it is omitted from this specification.
    [065] The secondary battery can be a lithium secondary battery.
    [066] The secondary battery can be used not only as a power source for small scale devices, but also as a power source for intermediate or large scale devices as described below.
    [067] The present invention also provides a battery module, including the secondary battery as a unit cell, and a battery case including the battery module.
    [068] The battery case can also be used as a power source for medium-scale or large-scale devices that require high temperature safety, a long lifespan, and high-speed properties. Petition 870190132678, 12/12 /2019, p. 24/34 17/21
    [069] Specific examples of intermediate or large scale devices include, but are not limited to, powered tools, which are powered by electric motors, electric vehicles (EVs) including hybrid electric vehicles (HEVs) and rechargeable hybrid electric vehicles (PHEVs ), two-wheel electric vehicles including electric bicycles (E-bikes) and electric scooters (E-scooters), electric golf carts and energy storage systems. BENEFITS
    [070] Since lithium titanium oxide (LTO) is used as an anode active material and a phosphate-based compound is used as an additive, a secondary battery, according to the present invention, obtains stabilization of electrode interface, thereby preventing the generation of gases and by-products. In this way, the secondary battery has not only high safety, but also an improved lifetime and high power characteristics. BRIEF DESCRIPTION OF THE DRAWINGS
    [071] The objects, aspects and other advantages mentioned above and others of the present invention will be understood more clearly from the detailed description presented below, taken in conjunction with the attached drawings, in which:
    [072] Figure 1 is a graph showing the comparison of cycle characteristics in a chamber at 45°C, according to experimental example 2; and
    [073] Figure 2 is a graph showing the comparison of gas generation intensity, associated with the period of time of storage at high temperature in a chamber at 60°C, according to experimental example 3. BEST WAY
    [074] The present invention will then be described by way of examples. However, it should be noted that the examples presented below are presented only to exemplify the present invention, without limiting its scope. Petition 870190132678, dated 12/12/2019, p. 25/34 18/21<Example 1>
    [075] An anode active material (Li1,33Ti1,67O4), a conductive material (Denka black) and a binder (PVdF) were added in a weight ratio of 95:2.5:2.5 to NMP, followed by mixing, to prepare an anodic mixture. The anodic mixture was then applied to a copper film, having a thickness of 20 µm, to form a coating layer, having a thickness of 60 µm, followed by lamination and drying, to produce an anode.
    [076] In addition, LiNi0.5Mn1.5O4, as a cathode active material, a conductive material (Denka black) and a binder (PVdF) were added in a weight ratio of 95:2.5:2.5 to NMP, followed by mixing, to prepare a cathodic mixture. The cathode mixture was then applied to a copper film, having a thickness of 20 µm, followed by lamination and drying, to produce a cathode.
    [077] A polyethylene membrane (Celgard, thickness: 20 μm) was then interposed as a separator, between the anode and the cathode, to form a set of electrodes. A liquid electrolyte with 1M LiPF6 dissolved in an EC/CMC solvent at a volume ratio of 1/2, to which a phosphate-based acrylate (R1 is H and n is 1 in formula 1) was added as a phosphate-based material. Phosphate at a content of 5% by weight, based on the total weight of the electrolyte, was injected into a pouch, in which the electrode assembly was mounted, to manufacture a pouch battery.<Example 2>
    [078] A pouch battery was manufactured in the same manner as in example 1, except that a pyrophosphate-based acrylate (R1 is H and n is 1 in formula 2) was used as a phosphate-based material.<Example 3>
    [079] A pouch battery was manufactured in the same manner as in example 1, except that dipentaerythritol pentaacrylate (DPentA) was added additionally, Petition 870190132678, 12/12/2019, p. 26/34 19/21 as a multifunctional compound to the electrolyte, at a content of 0.2% by weight, based on the weight of the solvent.<Example 4>
    [080] A pouch battery was manufactured in the same manner as in example 2, except that dipentaerythritol pentaacrylate (DPentA) was additionally added as a multifunctional compound to the electrolyte, at a content of 0.2% by weight, based on weight of the solvent.<Example 5>
    [081] A pouch battery was manufactured in the same manner as in example 1, except that 2,2'-azoisobutyronitrile (AIBN) was added as a polymerization initiator to the electrolyte at a content of 0.1% by weight, based in the weight of the solvent, after injection of the electrolyte, and a high temperature reaction was then conducted at a temperature of 70°C for 5 hours, to prepare a polymer gel electrolyte.<Example 6>
    [082] A pouch battery was manufactured in the same manner as in example 2, except that 2,2'-azoisobutyronitrile (AIBN) was added as a polymerization initiator to the electrolyte at a content of 0.1% by weight, based in the weight of the solvent, after injection of the electrolyte, and a high temperature reaction was then conducted at a temperature of 70°C for 5 hours, to prepare a polymer gel electrolyte.<Comparative example 1>
    [083] A pouch battery was manufactured in the same manner as in example 1, except that an electrolyte, without any phosphate-based acrylate (R1 is H and n is 1 in formula 1) added to it, was used.<Comparative example 2>
    [084] A pouch battery was manufactured in the same way as in the example Petition 870190132678, dated 12/12/2019, p. 27/34 20/212, except that an electrolyte was injected, after a phosphate-based acrylate (R1 is H and n is 1 in formula 1) was added to the electrolyte at a content of 40% by weight.<Experimental example 1>
    [085] The batteries (with a design capacity of 265 mAh), manufactured in examples 1 to 6 and in comparative examples 1 and 2, were subjected to a formation process at 2.75 V. The batteries were charged / discharged at a certain regime C, in a range between 1.6 V and 2.75 V, to check the discharge capacity. The results are shown in table 1 below.
    <Experimental example 2>
    [086] The cycle characteristics of the batteries manufactured in examples 1 to 3 and in comparative examples 1 and 2 were measured, while the batteries were charged / discharged at a C regime of 5 C, in a range between 1.6 V and 2 .75 V in a chamber at 45°C. The results are shown in Figure 1.<Experimental example 3>
    [087] The batteries (with a design capacity of 265 mAh), manufactured in examples 1 and 3 and in comparative examples 1 and 2, were subjected to a formation process at 2.75 V. The gas generation intensity per Parallel reaction was measured after the batteries were stored in a SOC of 100%, at a high temperature of 60°C. The results are shown in Figure 2.
    [088] As can be seen from Figures 2 and 3, comparative example 1 generated an excessive amount of gases and comparative example 2 degraded Petition 870190132678, of 12/12/2019, p. 28/34 21/21 significantly the characteristics of the cycle, while examples 1 to 6, according to the present invention, generated a small amount of gases, ensuring a high safety, and also presenting superior cycle characteristics.
    [089] As is evident from the description presented above, a secondary battery, according to the present invention, has several advantages. For example, since lithium titanium oxide (LTO) is used as an anode active material and a phosphate-based compound is used as an additive, the secondary battery achieves an interface stabilization, thereby preventing generation of gases and by-products. In this way, the secondary battery not only features high safety, but also an improved lifetime and high power characteristics.
    [090] It will be evident to those skilled in the art that various modifications and variations are possible in light of the teaching presented above, without departing from the scope of the invention. Petition 870190132678, 12/12/2019, p. 29/34 1/2
    权利要求:
    Claims (6)
    [0001]
    1. Secondary battery CHARACTERIZED by comprising a set of electrodes comprising a cathode, an anode and a separator interposed between them, and an electrolyte, in which the anode comprises lithium and titanium oxide (LTO), as an anode material active; and the electrolyte contains a phosphate-based compound as an additive and is a liquid electrolyte, wherein the phosphate-based compound comprises at least one selected from the group consisting of a phosphate-based acrylate of formula (1), an acrylate of formula (1). pyrophosphate base of the formula (2) and a phosphate-based urethane acrylate:
    [0002]
    2. Secondary battery according to claim 1, characterized in that the electrolyte contains 0.01 to 30% by weight of the phosphate-based compound, based on the total weight of the electrolyte.
    [0003]
    3. Secondary battery according to claim 1, CHARACTERIZED by the liquid electrolyte comprising an electrolyte serving as a plasticizer and a lithium salt. Petition 870210042799, dated 11/05/2021, p. 9/10 2/2
    [0004]
    4. Secondary battery according to claim 3, characterized in that the electrolyte contains 0.01 to 30% by weight of the lithium salt, based on the total weight of solid components included in the electrolyte.
    [0005]
    5. Battery module CHARACTERIZED by comprising the secondary battery, as defined in claim 1, as a unit cell.
    [0006]
    6. Battery case CHARACTERIZED by comprising the battery module as defined in claim 5.
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    同族专利:
    公开号 | 公开日
    WO2014010936A1|2014-01-16|
    IN2014DN10019A|2015-08-14|
    CN104380519B|2016-12-07|
    EP2874228A4|2016-03-02|
    KR20140008264A|2014-01-21|
    EP2874228A1|2015-05-20|
    US20180323471A1|2018-11-08|
    TWI485906B|2015-05-21|
    US20150079480A1|2015-03-19|
    KR101558861B1|2015-10-12|
    TW201411918A|2014-03-16|
    KR20150088773A|2015-08-03|
    BR112014030392A2|2017-07-25|
    EP2874228B1|2016-12-21|
    KR101586199B1|2016-01-19|
    JP2015525452A|2015-09-03|
    CN104380519A|2015-02-25|
    JP6042533B2|2016-12-14|
    US10862165B2|2020-12-08|
    US10056648B2|2018-08-21|
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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. |
    2019-09-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-02-17| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2021-05-25| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-06-08| B16A| Patent or certificate of addition of invention granted|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
    KR10-2012-0075153|2012-07-10|
    KR20120075153|2012-07-10|
    KR20120075818|2012-07-12|
    KR10-2012-0075818|2012-07-12|
    PCT/KR2013/006132|WO2014010936A1|2012-07-10|2013-07-10|Secondary battery comprising electrolyte additive|
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