WO2015065090A1 - 전극-분리막 복합체의 제조방법, 그 제조방법에 의해 제조된 전극-분리막 복합체 및 그를 포함하는 리튬 이차전지 - Google Patents
전극-분리막 복합체의 제조방법, 그 제조방법에 의해 제조된 전극-분리막 복합체 및 그를 포함하는 리튬 이차전지 Download PDFInfo
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- WO2015065090A1 WO2015065090A1 PCT/KR2014/010346 KR2014010346W WO2015065090A1 WO 2015065090 A1 WO2015065090 A1 WO 2015065090A1 KR 2014010346 W KR2014010346 W KR 2014010346W WO 2015065090 A1 WO2015065090 A1 WO 2015065090A1
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- electrode
- separator
- polymer particles
- composite
- separation film
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a method for producing an electrode-membrane composite, an electrode-membrane composite prepared by the method and a lithium secondary battery comprising the same, and more particularly, to directly coat a polymer solution including polymer particles on an electrode.
- the present invention relates to a method for producing an electrode-membrane composite, an electrode-membrane composite prepared by the method and a lithium secondary battery comprising the same.
- the electrochemical device is the area that is receiving the most attention in this respect, and the development of a secondary battery capable of charging and discharging has been the focus of attention, and in recent years in the development of such a battery in order to improve the capacity density and specific energy R & D on the design of electrodes and batteries is underway.
- lithium secondary batteries developed in the early 1990s have a higher operating voltage and greater energy density than conventional batteries such as Ni-MH, Ni-Cd, and sulfuric acid-lead batteries that use an aqueous electrolyte solution. I am in the spotlight.
- lithium ion batteries have safety problems such as ignition and explosion due to the use of the organic electrolyte, and are difficult to manufacture.
- the lithium ion polymer battery has been considered as one of the next generation batteries by improving the weakness of the lithium ion battery, but the capacity of the battery is still relatively low compared to the lithium ion battery, and the discharge capacity is improved due to insufficient discharge capacity at low temperatures. This is urgently needed.
- the porous separator of the lithium secondary battery has a problem of causing a short circuit between the positive electrode and the negative electrode due to the extreme heat shrinkage behavior at a temperature of about 100 °C or more due to the characteristics of the manufacturing process including the material properties and stretching.
- the battery is overcharged due to a charger malfunction or the like, and the voltage rises rapidly, excess lithium is precipitated at the positive electrode and excess lithium is inserted at the negative electrode, resulting in thermal instability of the positive electrode and the negative electrode.
- the organic solvent of the electrolyte is decomposed to cause a rapid exothermic reaction, a situation such as thermal runaway occurs suddenly, causing a serious damage to the stability of the battery.
- the separator of the lithium secondary battery should have excellent heat resistance at high temperature in order to prevent an internal short circuit, and in particular, shrinkage at high temperature should be minimized.
- the conventional lithium secondary battery is manufactured by being assembled in a state in which a polyolefin-based separator is interposed between the positive electrode and the negative electrode through a physical partition, the polyolefin-based separator has a problem that the thermal stability such as thermal shrinkage is weak.
- a lithium secondary battery including a separator having improved safety by forming a porous coating layer including inorganic particles on the upper surface of the polyolefin-based separator has been proposed.
- the separator having the porous coating layer including the inorganic particles and the electrode are assembled after being manufactured in a separate process, and thus, the efficiency of the process is somewhat reduced. have.
- the problem to be solved by the present invention is a method for producing an electrode-separation membrane composite, the electrode-manufactured by the manufacturing method of the present invention, which simplifies the manufacturing process by directly coating and drying a polymer solution containing polymer particles on the electrode. It is to provide a separator composite and a lithium secondary battery comprising the same.
- (S1) after applying the electrode active material slurry on at least one surface of the electrode current collector, and drying to form an electrode; (S2) coating a polymer solution including polymer particles on at least one surface of the electrode to form a separator coating layer; And (S3) drying the separator coating layer to form a porous separator.
- a method of manufacturing an electrode- separator composite is provided.
- the polymer particles may be an anionic polyelectrolyte.
- the polymer particles may be any one selected from the group consisting of polymethyl methacrylate, polystyrene, a copolymer containing methyl methacrylate as a monomer, and a copolymer containing styrene as a monomer, or two or more thereof. It may be a mixture.
- the size of the polymer particles may be 100 nm to 1 ⁇ m.
- the polymer particles may be a mixture of first polymer particles having a particle size of 100 nm to 300 nm and second polymer particles having a particle size of 500 nm to 1,000 nm at a weight ratio of 2: 8 to 3: 7. have.
- the polymer particles may have a functional group capable of collecting manganese on the surface thereof.
- the polymer solution acetone (acetone), methanol (methanol), ethanol (ethanol), tetra hydrofuran (tetra hydrofuran), methylene chloride (methylene chloride), chloroform (chloroform), dimethylform amide (dimethylform amide), N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, NMP), cyclohexane (cyclohexane) and may include a solvent which is any one selected from the group consisting of water or a mixture of two or more thereof. .
- the polymer solution may further include a binder.
- the solvent contained in the electrode active material slurry and the solvent contained in the polymer solution may be the same.
- the (S3) step may be performed through heat treatment or ultraviolet irradiation, in this case, the heat treatment temperature may be 70 to 120 °C.
- the pore size formed in the porous separator may be 50 nm to 500 nm.
- an electrode including an electrode current collector and an electrode active material layer formed on at least one surface of the electrode current collector; And a porous separator formed on at least one surface of the electrode and formed as a result of drying the separator coating layer including the polymer particles.
- An electrode- separator composite including a lithium secondary battery is provided.
- the polymer particles are coated on the electrode to form a porous separator, it is possible to effectively control the uniformity and flexibility of the pores.
- Method for producing an electrode-membrane composite according to the present invention is as follows.
- the electrode current collector may be any metal as long as it is a highly conductive metal used for a positive electrode or a negative electrode and is a metal to which an electrode active material slurry can easily adhere, and is not reactive in a voltage range of a lithium secondary battery.
- a non-limiting example of a positive electrode current collector is a foil prepared by aluminum, nickel or a combination thereof
- a non-limiting example of a negative electrode current collector is copper, gold, nickel or a copper alloy or a combination thereof
- the current collector may be used by stacking substrates made of the materials.
- the electrode active material slurry may be prepared by kneading using an electrode active material, a conductive material, a binder, and a solvent.
- an electrode After apply
- the electrode active material may be a positive electrode active material and a negative electrode active material commonly used in a lithium secondary battery.
- the conductive material is not particularly limited as long as it is an electronic conductive material that does not cause chemical change in the lithium secondary battery.
- carbon black, graphite, carbon fiber, carbon nanotubes, metal powder, conductive metal oxide, organic conductive materials, and the like can be used, and currently commercially available products as acetylene black series (Chevron Chemical) Chevron Chemical Company or Gulf Oil Company, etc., Ketjen Black EC series (Armak Company), Vulcan XC-72 (Cabot Company) (Cabot Company) and Super P (MMM).
- acetylene black, carbon black, graphite, etc. are mentioned.
- the binder may have a function of maintaining a positive electrode active material and a negative electrode active material in each current collector and connecting the active materials, and a binder commonly used may be used without limitation.
- a binder commonly used may be used without limitation.
- PVDF-co-HFP polyvinylidene fluoride-hexafluorofluoropropylene
- PVDF polyvinylidene fluoride
- PVDF polyacrylonitrile
- polymethyl methacrylate Various kinds of binders may be used, such as (polymethyl methacrylate), styrene-butadiene rubber (SBR), and carboxyl methyl cellulose (CMC).
- methanol ethanol
- ethanol ethanol
- N-methyl-2-pyrrolidone N-methyl-2-pyrrolidone
- acetone acetone
- tetra hydrofuran tetra hydrofuran
- Chloroform methylene chloride, dimethylform amide, water, cyclohexane and the like
- a polymer solution containing polymer particles is coated on at least one surface of the electrode to form a separator coating layer (S2).
- the polymer particles may be an anionic polyelectrolyte, wherein the anionic polyelectrolyte is polymethacrylate (PMA), polyacrylate (PA), polystyrenesulfonate (PSS), hyaluronic acid (HA) ) And a copolymer comprising a monomer constituting the polyelectrolyte.
- the copolymer may include polymethyl methacrylate, polystyrene, and methyl methacrylate as monomers. And it may be selected from the group consisting of a copolymer comprising styrene as a monomer.
- ions having positively charged functional groups such as manganese ions can be adsorbed, thereby preventing poisoning of manganese ions or the like at the cathode interface.
- a uniform micro level crystal lattice may be formed.
- the polymer particles may have a size of 100 nm to 1 ⁇ m, and when the numerical value is satisfied, the pore size of the porous separator formed by the polymer particles is 500 nm or less, more preferably 50 nm to 100 ⁇ m. It can be controlled at the level of nm.
- the polymer particles may be mixed with a first polymer particle having a particle size of 100 nm to 300 nm and a second polymer particle having a particle size of 500 nm to 1,000 nm at a weight ratio of 2: 8 to 3: 7. .
- the first polymer particles may be uniformly disposed between the second polymer particles, such that uniformity and degree of curvature may be uniform.
- the polymer particles may be attached to a functional group capable of collecting manganese on the surface. As a result, deterioration of battery performance can be prevented through the removal of manganese ions that can be poisoned to the negative electrode during the operation of the battery.
- the polymer solution is a solvent for dispersing the polymer particles, acetone (acetone), methanol (methanol), ethanol (ethanol), tetra hydrofuran (tetra hydrofuran), methylene chloride (chloroform), Dimethylform amide, N-methyl-2-pyrrolidone (NMP), cyclohexane and water, any one selected from the group consisting of or a mixture of two or more thereof Phosphorus solvents.
- the polymer solution may further include a binder.
- the binder used may be the same kind of binder as that used for the electrode active material slurry described above.
- a solvent included in the positive electrode and the negative electrode active material slurry, and the polymer solution may be those of the same system as each other.
- a solvent used in the cathode active material slurry may be used as the solvent of the polymer solution
- the anode active material The solvent used in the slurry (generally NMP, water, etc.) may be used as the solvent of the polymer solution.
- the separator coating layer is dried to form a porous separator (S3).
- heat treatment or ultraviolet irradiation may be performed, and through this process, the porosity of the porous separator may be appropriately adjusted, and the heat treatment temperature may be adjusted to obtain an appropriate porosity (40 to 60% level). It may be 70 to 120 °C.
- an electrode including an electrode current collector and an electrode active material layer formed on at least one surface of the electrode current collector; And a porous separator formed on at least one surface of the electrode and resulting from drying the separator coating layer including the polymer particles.
- the present invention there is no need to use a separate separator, and since the polymer particles are coated on the electrode to form a porous separator, the uniformity and flexibility of the pores can be effectively controlled.
- a lithium secondary battery comprising an electrode-separator composite according to the present invention.
- the electrode When the electrode-membrane composite is an anode-membrane composite, the electrode may be formed as an electrode assembly by further comprising a negative electrode, and in the case of a cathode-membrane composite, the electrode-membrane composite may be formed as an electrode assembly.
- the electrode assembly may be manufactured as a lithium secondary battery by being embedded in a battery case together with a nonaqueous electrolyte impregnating the electrode assembly.
- the electrolyte salt included in the nonaqueous electrolyte solution that can be used in the present invention is a lithium salt, and those lithium salts may be used without limitation, those conventionally used in a lithium secondary battery electrolyte.
- lithium salt anion F -, Cl -, Br - , 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) 3 C -, ( CF 3 SO 2) 3 C - , CF 3 ,
- organic solvent included in the nonaqueous electrolyte solution those conventionally used in a lithium secondary battery electrolyte solution may be used without limitation, and for example, ether, ester, amide, linear carbonate, cyclic carbonate, etc. may be used alone or two kinds. It can mix and use the above.
- carbonate compounds which are typically cyclic carbonates, linear carbonates, or mixtures thereof may be included.
- cyclic carbonate compound examples include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, vinylene carbonate, vinylethylene carbonate and any one selected from the group consisting of halides thereof or mixtures of two or more thereof.
- halides include, for example, fluoroethylene carbonate (FEC), but are not limited thereto.
- linear carbonate compound may be any one selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethylmethyl carbonate (EMC), methylpropyl carbonate and ethylpropyl carbonate. Mixtures of two or more of them may be representatively used, but are not limited thereto.
- ethylene carbonate and propylene carbonate which are cyclic carbonates among the carbonate-based organic solvents, are high viscosity organic solvents and have a high dielectric constant, so that they can dissociate lithium salts in the electrolyte better, and cyclic carbonates such as dimethyl carbonate and diethyl carbonate
- cyclic carbonates such as dimethyl carbonate and diethyl carbonate
- any one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, methylethyl ether, methylpropyl ether, and ethylpropyl ether, or a mixture of two or more thereof may be used. It is not limited to this.
- esters in the organic solvent include methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -valerolactone and One or a mixture of two or more selected from the group consisting of ⁇ -caprolactone may be used, but is not limited thereto.
- the injection of the nonaqueous electrolyte may be performed at an appropriate step in the manufacturing process of the lithium secondary battery according to the manufacturing process and required physical properties of the final product. That is, before the assembly of the lithium secondary battery or at the final stage of assembling the lithium secondary battery.
- the external shape of the lithium secondary battery according to the present invention is not particularly limited, but may be cylindrical, square, pouch type or coin type using a can.
- a polymer solution was prepared by dispersing 500 nm polystyrene particles in an aqueous solution to 20 wt%. Subsequently, the polymer solution was coated on the negative electrode at room temperature, and then the negative electrode coated with the polymer solution was dried in an oven at 70 to 120 ° C., and the polystyrene particles were fixed on the negative electrode to separate the negative electrode-membrane composite.
- the polymer solution was prepared by dispersing 500 nm polystyrene particles in an aqueous solution to 20 wt%. Subsequently, the polymer solution was coated on the negative electrode at room temperature, and then the negative electrode coated with the polymer solution was dried in an oven at 70 to 120 ° C., and the polystyrene particles were fixed on the negative electrode to separate the negative electrode-membrane composite.
- anode and the cathode-membrane composite were laminated to prepare an electrode assembly.
- Polystyrene particles of 500 nm and 100 nm were mixed at a ratio of 8: 2, and the polymer solution was prepared by dispersing the mixed polystyrene particles in an aqueous solution to 20% by weight. Subsequently, the polymer solution was coated on the negative electrode at room temperature, and then the negative electrode coated with the polymer solution was dried in an oven at 70 to 120 ° C., and the polystyrene particles were fixed on the negative electrode to separate the negative electrode-membrane composite.
- the polymer solution was prepared by dispersing the mixed polystyrene particles in an aqueous solution to 20% by weight. Subsequently, the polymer solution was coated on the negative electrode at room temperature, and then the negative electrode coated with the polymer solution was dried in an oven at 70 to 120 ° C., and the polystyrene particles were fixed on the negative electrode to separate the negative electrode-membrane composite.
- the polymer solution was prepared by dispersing the mixed polysty
- anode and the cathode-membrane composite were laminated to prepare an electrode assembly.
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
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- Engineering & Computer Science (AREA)
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- Materials Engineering (AREA)
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- Cell Separators (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
Claims (22)
- (S1) 전극 집전체의 적어도 일면에, 전극 활물질 슬러리를 도포한 후, 건조시켜 전극을 형성하는 단계;(S2) 고분자 입자를 포함하는 고분자 용액을 상기 전극의 적어도 일면에 코팅하여, 분리막 코팅층을 형성하는 단계; 및(S3) 상기 분리막 코팅층을 건조시켜 다공성의 분리막을 형성하는 단계;를 포함하는 전극-분리막 복합체의 제조방법.
- 제1항에 있어서,상기 고분자 입자는, 음이온성 폴리전해질인 것을 특징으로 하는 전극-분리막 복합체의 제조방법.
- 제1항에 있어서,상기 고분자 입자는, 폴리메틸메타크릴레이트, 폴리스타이렌, 메틸메타크릴레이트를 단량체로 포함하는 공중합체 및 스타이렌을 단량체로 포함하는 공중합체로 이루어진 군으로부터 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물인 것을 특징으로 하는 전극-분리막 복합체의 제조방법.
- 제1항에 있어서,상기 고분자 입자의 크기는, 100 nm 내지 1 ㎛인 것을 특징으로 하는 전극-분리막 복합체의 제조방법.
- 제1항에 있어서,상기 고분자 입자는, 입자크기가 100 nm 내지 300 nm인 제1 고분자 입자와, 입자크기가 500 nm 내지 1,000 nm인 제2 고분자 입자가 2:8 내지 3:7의 중량비로 혼합된 것을 특징으로 하는 전극-분리막 복합체의 제조방법.
- 제1항에 있어서,상기 고분자 입자는, 표면에 망간 포집이 가능한 관능기가 부착된 것을 특징으로 하는 전극-분리막 복합체의 제조방법.
- 제1항에 있어서,상기 고분자 용액은, 아세톤(acetone), 메탄올(methanol), 에탄올(ethanol), 테트라 하이드로퓨란(tetra hydrofuran), 메틸렌 클로라이드(methylene chloride), 클로로포름(chloroform), 디메틸포름 아미드(dimethylform amide), N-메틸-2-피롤리돈(N-methyl-2-pyrrolidone, NMP), 시클로헥산(cyclohexane) 및 물로 이루어진 군으로부터 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물인 용매를 포함하는 것을 특징으로 하는 전극-분리막 복합체의 제조방법.
- 제1항에 있어서,상기 고분자 용액은, 바인더를 더 포함하는 것을 특징으로 하는 전극-분리막 복합체의 제조방법.
- 제1항에 있어서,상기 전극 활물질 슬러리에 포함된 용매와, 상기 고분자 용액에 포함된 용매는 서로 동일한 것을 특징으로 하는 전극-분리막 복합체의 제조방법.
- 제1항에 있어서,상기 (S3) 단계는, 열처리 또는 자외선 조사를 통해 수행되는 것을 특징으로 하는 전극-분리막 복합체의 제조방법.
- 제10항에 있어서,상기 열처리 온도는, 70 내지 120 ℃인 것을 특징으로 하는 전극-분리막 복합체의 제조방법.
- 제1항에 있어서,상기 다공성의 분리막에 형성된 기공의 크기는, 50 nm 내지 500 nm인 것을 특징으로 하는 전극-분리막 복합체의 제조방법.
- 제1항 내지 제12항 중 어느 한 항의 제조방법에 의해 제조된 전극-분리막 복합체.
- 전극 집전체 및 전극 집전체의 적어도 일면에 형성된 전극 활물질층을 포함하는 전극; 및상기 전극의 적어도 일면에 형성되며, 고분자 입자를 포함하는 분리막 코팅층의 건조 결과물인 다공성의 분리막;을 포함하는 전극-분리막 복합체.
- 제14항에 있어서,상기 고분자 입자는, 음이온성 폴리전해질인 것을 특징으로 하는 전극-분리막 복합체.
- 제14항에 있어서,상기 고분자 입자는, 폴리메틸메타크릴레이트, 폴리스타이렌, 메틸메타크릴레이트를 단량체로 포함하는 공중합체 및 스타이렌을 단량체로 포함하는 공중합체로 이루어진 군으로부터 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물인 것을 특징으로 하는 전극-분리막 복합체.
- 제14항에 있어서,상기 고분자 입자의 크기는, 100 nm 내지 1 ㎛인 것을 특징으로 하는 전극-분리막 복합체.
- 제14항에 있어서,상기 고분자 입자는, 입자크기가 100 nm 내지 300 nm인 제1 고분자 입자와, 입자크기가 500 nm 내지 1,000 nm인 제2 고분자 입자가 2:8 내지 3:7의 중량비로 혼합된 것을 특징으로 하는 전극-분리막 복합체.
- 제14항에 있어서,상기 고분자 입자는, 표면에 망간 포집이 가능한 관능기가 부착된 것을 특징으로 하는 전극-분리막 복합체.
- 제14항에 있어서,상기 분리막 코팅층은, 바인더를 더 포함하는 것을 특징으로 하는 전극-분리막 복합체.
- 제14항에 있어서,상기 다공성의 분리막에 형성된 기공의 크기는, 50 nm 내지 500 nm인 것을 특징으로 하는 전극-분리막 복합체.
- 제14항 내지 제21항 중 어느 한 항의 전극-분리막 복합체를 포함하는 리튬 이차전지.
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JP2016521323A JP6306168B2 (ja) | 2013-10-31 | 2014-10-31 | 電極−分離膜複合体の製造方法、その製造方法によって製造された電極−分離膜複合体及びそれを含むリチウム二次電池 |
US14/772,321 US11450925B2 (en) | 2013-10-31 | 2014-10-31 | Method of manufacturing electrode-separator composite, electrode-separator composite manufactured by the manufacturing method and lithium secondary battery comprising the same |
CN201480018763.7A CN105074989B (zh) | 2013-10-31 | 2014-10-31 | 电极-隔膜复合物的制造方法、由该制造方法制造的电极-隔膜复合物及包含其的锂二次电池 |
EP14858676.1A EP2953201B1 (en) | 2013-10-31 | 2014-10-31 | Method for manufacturing electrode-separation film complex, electrode-separation film complex manufactured by manufacturing method therefor and lithium secondary battery comprising same |
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KR102570263B1 (ko) * | 2016-10-14 | 2023-08-24 | 삼성에스디아이 주식회사 | 리튬 전지용 전극, 이를 포함하는 리튬 전지, 및 상기 리튬 전지의 제조방법 |
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JP6992701B2 (ja) * | 2018-08-06 | 2022-01-13 | トヨタ自動車株式会社 | セパレータ一体型電極の製造方法、及び、セパレータ一体型電極 |
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TWI570993B (zh) | 2017-02-11 |
US11450925B2 (en) | 2022-09-20 |
CN105074989A (zh) | 2015-11-18 |
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