WO2023008803A1 - 이차 전지용 전극, 이의 제조방법, 및 상기 전극을 포함하는 이차 전지 - Google Patents
이차 전지용 전극, 이의 제조방법, 및 상기 전극을 포함하는 이차 전지 Download PDFInfo
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- WO2023008803A1 WO2023008803A1 PCT/KR2022/010468 KR2022010468W WO2023008803A1 WO 2023008803 A1 WO2023008803 A1 WO 2023008803A1 KR 2022010468 W KR2022010468 W KR 2022010468W WO 2023008803 A1 WO2023008803 A1 WO 2023008803A1
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- electrode
- secondary battery
- binder
- acrylic
- polytetrafluoroethylene
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- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0433—Molding
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
- H01M4/623—Binders being polymers fluorinated 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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 a secondary battery electrode, a manufacturing method thereof, and a secondary battery including the electrode.
- the electrochemical device is the field that is attracting the most attention in this respect, and among them, the development of a secondary battery capable of charging and discharging has become a focus of attention.
- research and development on the design of new electrodes and batteries have been actively conducted in order to improve capacity density and specific energy in the development of secondary batteries.
- lithium secondary batteries are in the limelight due to their high operating voltage and significantly higher energy density than conventional batteries.
- An electrode for a secondary battery is usually manufactured by laminating an electrode active material layer formed by binding an active material and a conductive material used as necessary with a binder on a current collector.
- a method in which a slurry containing an electrode active material, a binder, a conductive material, etc. is coated on a current collector and the solvent is removed by heat or the like is generally used.
- the method has a disadvantage in that the solvent must be removed from the electrode slurry, and thus economic feasibility and productivity are lowered.
- a method of manufacturing an electrode without using an electrode slurry has been proposed. That is, a technique of manufacturing an electrode film by mixing an active material, a binder, and a conductive material without a liquid medium such as a solvent or a dispersion medium and then passing the powder mixture through a rolling roll is being actively developed.
- binders called “fibrillizable binders” or fibril-forming binders are used. The binder binds the active material and the conductive material while being fibrillated, thereby freeing - Enables the manufacture of a standing electrode film
- the electrode film manufactured in this way is used in the manufacture of an electrode in a way of being laminated on a current collector.
- the conventional method as described above provides various advantages compared to the method of applying slurry for an electrode.
- the method has disadvantages in that the dough becomes very hard when the particle size of the active material is small, making subsequent processing difficult and brittle due to lack of flexibility.
- the present invention has been made to solve the above problems of the prior art, and an object of the present invention is to provide an electrode for a secondary battery including an active material having a small particle size, excellent flexibility, and a dry electrode film with minimized breakage. to be
- an object of the present invention is to provide a method for manufacturing an electrode for a secondary battery capable of efficiently manufacturing the electrode.
- an object of the present invention is to provide a secondary battery having excellent driving characteristics and lifespan characteristics by including the electrode.
- a dry electrode film comprising an active material having an average particle diameter of 0.05 ⁇ m to 3 ⁇ m, a conductive material, and a fibrillated binder; and a current collector in which the electrode film is laminated.
- the present invention provides a secondary battery including the electrode.
- the electrode for a secondary battery of the present invention provides excellent quality by including an active material having a small particle size, yet having excellent flexibility and minimizing breakage.
- the method of manufacturing an electrode for a secondary battery of the present invention provides an effect of greatly improving the manufacturing efficiency of the electrode.
- the secondary battery of the present invention provides excellent driving characteristics and lifespan characteristics by including the electrode.
- 1 is an image taken of the form of a fibrillated binder included in an electrode as an embodiment of the present invention
- Figure 2 is a view schematically showing the structure of a free-standing film produced according to the particle size of the active material
- FIG. 3 is a view schematically showing a manufacturing form of a free-standing film in the case of using one type of fibrillable binder as an embodiment of the present invention
- FIG. 4 is a diagram schematically illustrating a manufacturing form of a free-standing film in the case of using two or more types of fibrillable binders having different glass transition temperatures as an embodiment of the present invention.
- Example 5 is a photograph of the shape of a free-standing film prepared in Example 1 as an embodiment of the present invention.
- An electrode for a secondary battery of the present invention includes a dry electrode film including an active material having an average particle diameter of 0.05 ⁇ m to 3 ⁇ m, a conductive material, and a fibrillated binder; and a current collector in which the electrode film is laminated.
- the particle diameter of the active material included in the electrode decreases, the degree of integration of the active material in the electrode increases and the load amount of the active material per unit volume increases, so the energy density increases, which is advantageous in terms of battery capacity. Therefore, there is a need for the use of an active material having a small particle diameter in the manufacture of an electrode.
- the above electrode was manufactured for the first time.
- the electrode manufactured in the present invention provides an effect of improving driving characteristics and life characteristics of a battery.
- the average particle diameter of the active material may be set based on D50.
- the electrode for a secondary battery of the present invention may be an anode or a cathode.
- the fibrillated binder may include polytetrafluoroethylene.
- the fibrillated binder may further include acrylic-modified polytetrafluoroethylene.
- the acrylic-modified polytetrafluoroethylene refers to a binder in which properties of polytetrafluoroethylene are modified by mixing polytetrafluoroethylene with an acrylic polymer.
- the acrylic-modified polytetrafluoroethylene may perform a function of improving strength and flexibility of a free-standing film because the acrylic binder provides excellent adhesion at a glass transition temperature or higher.
- the polytetrafluoroethylene and the acrylic polymer may be mixed in a weight ratio of 7:3 to 3:7, preferably in a weight ratio of 6:4 to 4:6.
- Polytetrafluoroethylene included in the acrylic-modified polytetrafluoroethylene is a polymer capable of fibrillation, and for example, one having a high molecular weight having a melt viscosity of 108 poises or more at 380° C. may be used. Also, when expressed in standard specific gravity (ASTM D-1457), those having a standard specific gravity of 2.210 or less, preferably 2.200 to 2.130 may be used.
- the acrylic polymer is, for example, a hydrocarbon-based monomer that is liquid at room temperature, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, iso ⁇ , ⁇ -ethylenically unsaturated carboxylic acid esters such as propyl acrylate, isopropyl methacrylate, lauryl acrylate and stearyl acrylate; hydroxyalkyl esters of ⁇ , ⁇ -ethylenically unsaturated carboxylic acids such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 3-hydroxypropyl methacrylate; alkoxyalkyl esters of ⁇ , ⁇ -ethylenically unsaturated carboxylic acids such as diethylene glycol methacrylate; ⁇ , ⁇ -ethylenically unsaturated carboxylic acid amides such as
- the acrylic-modified polytetrafluoroethylene for example, a powder form may be used, and specifically, Metabran A-3000 manufactured by Mitsubishi Rayon Co., Ltd. may be used.
- the structure of the powder may be, for example, a mixture of polytetrafluoroethylene and an acrylic polymer to exist in a matrix form, or a form in which an acrylic polymer is coated on polyterafluoroethylene.
- the acrylic-modified polytetrafluoroethylene may have a glass transition temperature of greater than 60°C.
- the fibrillated binder contains polytetrafluoroethylene and the acrylic-modified polytetrafluoroethylene in a ratio of 1:9 to 9:1, preferably 3:7 to 7:3. It can be included in weight ratio.
- the average particle diameter of the active material may be 0.05 ⁇ m to 2 ⁇ m, and 0.05 ⁇ m to 1.5 ⁇ m may be used.
- the dry electrode film is prepared by preparing a dry electrode dough by primary fibrillation of a fibrillable binder, powdering by pulverizing the dry electrode dough, and pressing the powders. During formation of the dry electrode film, fibers fibrillated in multiple directions by secondary fibrillation of the fibrillable binder may be included.
- the method for manufacturing an electrode for a secondary battery of the present invention is characterized in that it includes the following steps.
- the powder may have a particle size of 100 ⁇ m to 1000 ⁇ m, more preferably 300 ⁇ m to 1000 ⁇ m. Manufacturing the powder particle diameter less than 100 ⁇ m is difficult in the process, and the effect thereof is limited, so it is not preferable, and when it exceeds 1000 ⁇ m, it is difficult to form a uniform thickness and rolling density when manufactured in the form of a film. may occur, which is not desirable.
- the fibrillable binder means a binder that can be fibrous by the addition of shear force.
- the fibrillable binder may include polytetrafluoroethylene.
- the fibrillable binder may further include acrylic-modified polytetrafluoroethylene.
- the acrylic-modified polytetrafluoroethylene may have a glass transition temperature of greater than 60°C. If the glass transition temperature is lower than the above temperature, the acrylic-modified polytetrafluoroethylene is fibrous in the (b) dough preparation step, and then the dry electrode dough is pulverized in the powder preparation step (c) to become a powder state, so that the acrylic The meaning of further adding modified polytetrafluoroethylene is halved. That is, in one embodiment of the present invention, as shown in FIG. 4, the acrylic-modified polytetrafluoroethylene is not fibrous in the (b) dough preparation step due to the glass transition temperature, and (d) in the film forming step. It is preferable to be fibrous.
- the dry electrode film manufactured according to the present invention can be manufactured to have high MD (Machine Direction) and TD (Transverse Direction) strength. Furthermore, the dry electrode film manufactured according to the present invention may have a form in which the fibrillable binder is multi-directionally fibrous.
- the dough preparation step (b) may be carried out at a temperature higher than the glass transition temperature or the glass transition temperature of polytetrafluoroethylene, specifically carried out in the range of 30 to 60 ° C. It can be.
- the upper temperature limit is preferably lower than the glass transition temperature of acrylic-modified polytetrafluoroethylene.
- the (d) film forming step may be performed at the glass transition temperature of acrylic-modified polytetrafluoroethylene or at a temperature higher than the glass transition temperature, and may be specifically performed in a range of greater than 60 °C to 120 °C. .
- the fibrillable binder contains polytetrafluoroethylene and the acrylic-modified polytetrafluoroethylene in a ratio of 1:9 to 9:1, preferably 3:7 to 7:3. may be included in weight ratio.
- the manufactured dry electrode film may have high strength in both MD (Machine Direction) direction and TD (Transverse Direction) direction, and furthermore, be fibrous in multiple directions to have high strength in all directions. It is desirable because you can have it.
- a secondary battery including the electrode of the present invention is provided.
- the secondary battery may be a lithium secondary battery.
- the active material all components commonly used in positive electrodes and negative electrodes may be used.
- the active material is a cathode active material
- M1 and M2 are each independently Al, Ni , Co, Fe, Mn, V, Cr, Ti, W, Ta, Mg, and Mo
- x, y, and z are independently atomic fractions of oxide composition elements, 0 ⁇ x ⁇ 0.5 , 0 ⁇ y ⁇ 0.5, 0 ⁇ z ⁇ 0.5, 0 ⁇ x+y+z ⁇ 1)
- any one active material particle selected from the group consisting of or a mixture of two or more of them may be included.
- the electrode active material is a negative electrode active material
- natural graphite or artificial graphite mesophase carbon microbeads (MCMB, pyrolytic carbon), mesophase pitch based carbon fiber, mesophase pitch carbonaceous materials such as pitches), petroleum or coal tar pitch derived cokes, etc.
- the active material may be included in, for example, 85 to 98% by weight based on the total weight of the electrode film.
- the conductive material is not particularly limited as long as it has conductivity without causing chemical change in the secondary battery.
- carbon black such as carbon black, acetylene black, Ketjen black, channel black, farnes black, lamp black, and thermal black
- metal powders such as aluminum and nickel powder
- conductive whiskers such as zinc oxide and potassium titanate
- conductive metal oxides such as titanium oxide
- At least one selected from polyphenylene derivatives and the like may be used.
- the conductive material may be included in, for example, 1 to 10% by weight, specifically 2 to 4% by weight, based on the total weight of the electrode film.
- the present invention may further include other binders in addition to the fibrillated binder or the fibrillable binder.
- the other binder is a component that assists in the bonding of the active material and the conductive material and the adhesion to the current collector, and any material that can be used for an electrode can be used without limitation.
- a non-acrylic polymer or an acrylic polymer may be used as the binder.
- any polymer including at least one repeating unit of the binder polymer derived from an acrylic monomer may be used without limitation.
- the acrylic monomer include alkyl acrylate, alkyl methacrylate, isoalkyl (meth) acrylate, and the like.
- alkyl may be an alkyl group having 1 to 10 carbon atoms, and more specifically, 1 to 5 carbon atoms. It may be an alkyl group of two.
- acrylic monomer examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and pentyl (meth) acrylate.
- the acrylic polymer may be a homopolymer composed of one type of repeating unit derived from an acrylic monomer, a copolymer including repeating units derived from two or more types of acrylic monomers, or a mixture of two or more types thereof.
- the acrylic polymer is acrylate-styrene-butadiene rubber, acrylate-acrylonitrile-styrene-butadiene rubber, methyl acrylate-styrene-butadiene rubber, methyl acrylate-acrylonitrile-styrene-butadiene rubber, ethyl acryl Late-styrene-butadiene rubber, ethyl acrylate-acrylonitrile-styrene-butadiene rubber, propyl acrylate-styrene-butadiene rubber, propyl acrylate-acrylonitrile-styrene-butadiene rubber, butyl acrylate-styrene-butadiene rubber and at least one selected from the group consisting of butyl acrylate-acrylonitrile-styrene-butadiene rubber and the like, and may be a copolymer of at least one non-acrylic monomer and an acrylate-
- the acrylic polymer may be a mixture of two or more types of homoacrylic polymers, a mixture of two or more types of acrylic copolymers, a mixture of a copolymer of two or more types of non-acrylic monomers and acrylate monomers, and furthermore, a homoacrylic polymer, It may be a mixture of two or more of an acrylic copolymer and a copolymer of a non-acrylic monomer and an acrylate monomer.
- the non-acrylic polymer refers to a polymer containing one or more types of repeating units derived from a non-acrylic monomer, and specifically, a homopolymer composed of one type of repeating unit, a copolymer containing two or more different types of repeating units, and a different type of repeating unit. It may be a mixture of two or more homopolymers, or a mixture of two or more of them.
- non-acrylic polymer examples include styrene-butadiene rubber (SBR), a mixture of polystyrene and polybutadiene, polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (polyvinylidene fluoride-cohexafluoropropylene), polyvinylidene fluoride-cotrichloroethylene, polytetrafluoroethylene (PTFE), polyvinylpyrrolidone, polyethylene oxide, polyarylate ( polyarylate), cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cyanoethylpullulan, cyanoethylpolyvinylalcohol, Cyanoethyl cellulose (cyanoethylcellulose), cyanoethyl sucrose (cyanoethylsucrose), pullulan (pullulan), and carboxyl
- the total binder content including the fibrillated binder may be 0.1 to 10% by weight, specifically 1 to 4% by weight based on the total weight of the electrode film.
- the content of the binder satisfies this range, the adhesion between the electrode active material layer and the current collector is improved, the electrode resistance is reduced due to the improvement in adhesion, or electrode detachment can be prevented even after cell degeneration, and the binder moves to the electrode surface ( migration) to improve the ion conductivity or electrical conductivity in the electrode.
- a known current collector used in a secondary battery may be used without limitation.
- stainless steel, aluminum, nickel, titanium, calcined carbon, copper; stainless steel surface treated with carbon, nickel, titanium or silver; aluminum-cadmium alloy; Non-conductive polymer surface treated with a conductive material; Non-conductive polymer surface treated with metal; and conductive polymers may be used.
- a method of manufacturing an electrode for a secondary battery according to an embodiment of the present invention may include the following steps.
- the mixing in the step (a) means mixing in the absence of a solvent.
- the dry mixing may be performed by mixing for 0.5 to 10 minutes at 600 rpm to 20000 rpm, more specifically, 1000 rpm to 12000 rpm at room temperature or lower using a stirring device.
- the shear mixing of the step (b) may include applying a high shear force by shear compressing the mixture.
- a high shear force may be applied by shear-compressing the mixture at 10 rpm to 100 rpm for 1 to 10 minutes.
- PBV-0.1L Irie Shokai Co.
- high shear force may be applied by shear-compressing the mixture at 10 rpm to 100 rpm for 1 to 10 minutes.
- the high shear force may be 50N to 1000N, specifically 100N to 500N, and more specifically 100N to 300N.
- the powder may have a particle size of 100 ⁇ m to 1000 ⁇ m.
- step (d) Pressing in the step of forming the free-standing film of step (d) may be performed using a Two roll mill MR-3 (Inoue Company) or the like.
- the (e) step of laminating the free-standing film on the current collector may include positioning the free-standing film on the current collector and rolling it, wherein the rolling is performed using a roll press method. can be done through
- the present invention relates to a secondary battery including a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode, wherein at least one of the positive electrode and the negative electrode is the aforementioned electrode.
- the electrode according to the present invention is used as only one of the positive electrode and the negative electrode, other electrodes known in the art may be used without limitation.
- the secondary battery will be described as an example. Specifically, a lithium secondary battery will be described as an example.
- the separator is a porous polymer film commonly used as a separator in a lithium secondary battery, for example, polyolefins such as ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer, and ethylene/methacrylate copolymer.
- a porous polymer film made of a polymer-based polymer may be used alone or laminated.
- an insulating thin film having high ion permeability and mechanical strength may be used.
- the separator may include a safety reinforced separator (SRS) having an organic/inorganic composite porous coating layer thinly coated by connecting and fixing inorganic particles to the surface of a separator substrate such as a porous polymer film through a binder polymer.
- SRS safety reinforced separator
- conventional porous non-woven fabrics for example, non-woven fabrics made of high melting point glass fibers, polyethylene terephthalate fibers, etc. may be used, and a form in which the above-described organic/inorganic composite porous coating layer is applied to the porous non-woven fabric is also possible, and is limited thereto. it is not going to be
- the lithium secondary battery of the present invention may be manufactured by accommodating the positive and negative electrode assemblies in a battery case and injecting an electrolyte.
- the electrolyte may include a lithium salt and an organic solvent for dissolving the lithium salt.
- the lithium salt any one commonly used in an electrolyte for a secondary battery may be used without limitation.
- an anion of the lithium salt F - , Cl - , I - , NO 3 - , N(CN) 2 - , BF 4 - , ClO 4 - , PF 6 - , (CF 3 ) 2 PF 4 - , (CF 3 ) 3 PF 3 - , (CF 3 ) 4 PF 2 - , (CF 3 ) 5 PF - , (CF 3 ) 6 P - , CF 3 SO 3 - , CF 3 CF 2 SO 3 - , (CF 3 SO 2 ) 2 N - , (FSO 2 ) 2 N - , CF 3 CF 2 (CF 3 ) 2 CO - , (CF 3 SO 2 ) 2 CH - , (SF 5 )
- the organic solvent included in the electrolyte may be used without limitation as long as it is used in this field, and representative propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, methylpropyl carbonate, dipropyl carbonate, dimethyl At least one selected from the group consisting of sulfoxide, acetonitrile, dimethoxyethane, diethoxyethane, vinylene carbonate, sulfolane, gamma-butyrolactone, propylene sulfite, and tetrahydrofuran may be used.
- ethylene carbonate and propylene carbonate which are cyclic carbonates
- a low-viscosity, low-dielectric constant linear carbonate such as carbonate is mixed and used in an appropriate ratio, an electrolyte solution having high electrical conductivity can be prepared and can be more preferably used.
- the electrolyte stored according to the present invention may further include an additive such as an overcharge inhibitor included in a conventional electrolyte solution.
- an additive such as an overcharge inhibitor included in a conventional electrolyte solution.
- electrolyte a known solid electrolyte may be used.
- a secondary battery according to an embodiment of the present invention may be a stack type, a winding type, a stack and folding type, or a cable type.
- the secondary battery may be used as a battery cell used as a power source for a small device, and may also be used as a unit cell in a medium or large battery module including a plurality of battery cells.
- the medium-to-large-sized device include an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, and a power storage system.
- it is useful for hybrid electric vehicles and batteries for renewable energy storage, which are areas where high power is required. can be used
- configurations and manufacturing methods known in the art may be applied to parts not described above without limitation.
- LFP powder (trade name DY-3, Dynanonic Co.), which is a positive electrode active material particle with an average particle diameter of 1.08 ⁇ m
- 2 g of Li250 (Denka Co.) as a conductive material 1 g
- PTFE as a binder
- acryl-modified PTFE trade name A3800, Mitsubishi Co.
- 1 g was mixed for 1 minute at 5000 rpm without a solvent using a Lab Blender (Waring Co.) as a blender (first mixing).
- high shear mixing was performed (secondary mixing) by applying a shear force of 250N to the mixture at a temperature of 50° C. (PBV-0.1L, Irie Shokai Co.).
- the dough-like secondary mixture was pulverized using a grinder (trade name: ZM200, Retsch Co.), and sieved to prepare a powdery mixture having a particle size of 300 ⁇ m to 1000 ⁇ m.
- the powdered mixture was pressurized (Two roll mill MR-3, Inoue Co.) to prepare a free-standing film.
- the sheeting was performed by setting the temperature of the rolls of the Two roll mill MR-3 to 70 ° C. Thereafter, the free-standing film was placed on one surface of an aluminum current collector having a thickness of 15 ⁇ m and pressed to prepare a positive electrode.
- Example 1 the secondary mixture in the form of dough was pressed (Two roll mill MR-3, Inoue Co.) without the process of preparing a mixture in a powder state by grinding and sieving, and the manufacturing process was performed as a free-standing film.
- a positive electrode was manufactured in the same manner as in Example 1, except that only “2 g of PTFE” was used instead of “1 g of PTFE and 1 g of acrylic-modified PTFE” as a binder in Example 1.
- a positive electrode was prepared in the same manner as in Example 1, except that the second mixing was performed at 100 °C in Example 1.
- Example 1 The flexibility of the free-standing films prepared in Example 1, Comparative Example 2, and Comparative Example 3 was measured in the longitudinal and The flexibility was measured while gradually reducing the diameter of the cylindrical device for each transverse direction, and the diameter at which cracking began was measured. The measurement results are shown in Table 1 below.
- Example 1 In order to measure the longitudinal and transverse tensile strengths of the free-standing films prepared in Example 1, Comparative Example 2, and Comparative Example 3, electrodes having a width of 20 mm, a length of 200 mm, and a thickness of 200 ⁇ m were sampled. Tensile strength of the samples was measured at 50 mm/min by a 180-degree peel measurement method using Instron's UTM equipment. During the measurement, the maximum value of the force applied to the point at which cracks did not occur in the film was evaluated as the strength of the free-standing film, and the measurement results are shown in Table 1 below.
- Example 2 and Comparative Example 4 Preparation of a lithium secondary battery
- Example 2 and Comparative Example 4 were prepared using the positive electrodes prepared in Example 1 and Comparative Example 3, respectively.
- the specific manufacturing method is as follows.
- negative electrode active materials natural graphite, carbon black conductive material, and PVdF binder were mixed in a weight ratio of 85:10:5 in an N-methylpyrrolidone solvent to prepare a composition for forming a negative electrode, and the composition was applied to a copper current collector to form a negative electrode. was manufactured.
- An electrode assembly was prepared by interposing a porous polyethylene separator between the positive electrode prepared in Example 1 or Comparative Example 3 and the negative electrode prepared in (1) above, and after placing the electrode assembly inside the case, the electrolyte was poured into the case. was injected to prepare a lithium secondary battery.
- Example 2 and Comparative Example 4 prepared above were charged and discharged to evaluate capacity retention rates, which are shown in Table 2 below.
- the 1st and 2nd cycles were charged and discharged at 0.1C, and the 3rd to 49th cycles were charged and discharged at 0.5C.
- the 50th cycle was terminated in the state of charge (with lithium in the negative electrode).
- Capacity retention rate (%) (49 discharge capacity / 1 discharge capacity) ⁇ 100
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Abstract
Description
유연성
(갈라짐 발생 지름 mm) |
인장강도 | |||
종방향 | 횡방향 | 종방향 | 횡방향 | |
실시예 1 프리-스탠딩 필름 | 3 | 5 | 6.5 | 3.1 |
비교예 2 프리-스탠딩 필름 | 3 | 25 | 6.2 | 0.7 |
비교예 3 프리-스탠딩 필름 | 3 | 30 | 5.9 | 0.4 |
용량 유지율(%) | |
실시예 2 리튬 이차 전지 | 97.4 |
비교예 4 리튬 이차 전지 | 97.0 |
Claims (15)
- 평균 입경이 0.05㎛ 내지 3㎛인 활물질, 도전재, 및 피브릴화된 바인더를 포함하는 건식 전극 필름; 및 상기 전극 필름이 적층된 집전체;를 포함하는 이차 전지용 전극.
- 제1항에 있어서,상기 피브릴화된 바인더는 폴리테트라플루오로에틸렌을 포함하는 것을 특징으로 하는 이차 전지용 전극.
- 제2항에 있어서,상기 피브릴화된 바인더는 아크릴 변성 폴리테트라플루오로에틸렌을 더 포함하는 것을 특징으로 하는 이차 전지용 전극.
- 제3항에 있어서,상기 피브릴화된 바인더는 폴리테트라플루오로에틸렌과 상기 아크릴 변성 폴리테트라플루오로에틸렌이 1:9 내지 9:1의 중량비로 포함하는 것을 특징으로 하는 이차 전지용 전극.
- 제3항에 있어서,상기 아크릴 변성 폴리테트라플루오로에틸렌은 폴리테트라플루오로에틸렌과 아크릴계 고분자가 7:3 내지 3:7의 중량비로 혼합된 것을 특징으로 하는 이차 전지용 전극.
- 제1항에 있어서,상기 활물질의 평균 입경이 0.05㎛ 내지 2㎛인 것을 특징으로 하는 이차 전지용 전극.
- 제1항에 있어서,상기 건식 전극 필름이, 피브릴화 가능 바인더의 1차 피브릴화에 의한 건식 전극 반죽 제조, 상기 건식 전극 반죽의 분쇄에 의한 분말화, 및 상기 분말들의 가압에 의한 건식 전극 필름 성형시 피브릴화 가능 바인더의 2차 피브릴화에 의해 다방향으로 피브릴화된 섬유를 포함하는 것을 특징으로 하는 이차 전지용 전극.
- (a) 평균 입경이 0.05㎛ 내지 3㎛인 활물질, 도전재, 및 피브릴화 가능 바인더를 혼합하는 단계;(b) 상기 혼합물에 대하여 전단 믹싱을 수행하여 피브릴화 가능 바인더를 섬유화시켜서 건식 전극 반죽을 제조하는 단계;(c) 상기 건식 전극 반죽을 분쇄하여 분말 상태로 제조하는 단계;(d) 상기 분말들을 가압하여 프리 스탠딩 필름 형태로 성형하는 단계; 및(e) 상기 프리 스탠딩 필름을 집전체 상에 적층하는 단계;를 포함하는 이차 전지용 전극의 제조방법.
- 제8항에 있어서,상기 (c) 단계에서 분말은 입경이 100㎛ 내지 1000㎛인 것을 특징으로 하는 이차 전지용 전극의 제조방법.
- 제8항에 있어서,상기 피브릴화 가능 바인더는 폴리테트라플루오로에틸렌을 포함하는 것을 특징으로 하는 이차 전지용 전극의 제조방법.
- 제10항에 있어서,상기 피브릴화 가능 바인더는 아크릴 변성 폴리테트라플루오로에틸렌을 더 포함하는 것을 특징으로 하는 이차 전지용 전극의 제조방법.
- 제11항에 있어서,상기 피브릴화 가능 바인더는 폴리테트라플루오로에틸렌과 상기 아크릴 변성 폴리테트라플루오로에틸렌을 1:9 내지 9:1의 중량비로 포함하는 것을 특징으로 하는 이차 전지용 전극의 제조방법.
- 제11항에 있어서,상기 아크릴 변성 폴리테트라플루오로에틸렌은 폴리테트라플루오로에틸렌과 아크릴계 고분자가 7:3 내지 3:7의 중량비로 혼합된 것을 특징으로 하는 이차 전지용 전극의 제조방법.
- 제11항에 있어서,상기 (b) 단계는 폴리테트라플루오로에틸렌의 유리전이온 또는 상기 유리전이온도보다 높고, 아크릴 변성 폴리테트라플루오로에틸렌의 유리전이온도보다 낮은 온도에서 수행되며,상기 (d) 단계는 아크릴 변성 폴리테트라플루오로에틸렌의 유리전이온도 또는 상기 유리전이온도 보다 높은 온도에서 수행되는 것을 특징으로 하는 이차 전지용 전극의 제조방법.
- 제1항의 전극을 포함하는 이차 전지.
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EP22849779.8A EP4243113A1 (en) | 2021-07-30 | 2022-07-18 | Electrode for secondary battery, method for manufacturing same, and secondary battery comprising electrode |
CN202280008222.0A CN116783728A (zh) | 2021-07-30 | 2022-07-18 | 二次电池用电极、其制造方法和包含该电极的二次电池 |
JP2023546327A JP2024505952A (ja) | 2021-07-30 | 2022-07-18 | 二次電池用電極、この製造方法、及び前記電極を含む二次電池 |
US18/281,765 US20240162444A1 (en) | 2021-07-30 | 2022-07-18 | Electrode for secondary battery, method of manufacturing the same and secondary battery comprising the same |
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KR20230018802A (ko) | 2023-02-07 |
JP2024505952A (ja) | 2024-02-08 |
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