WO2016099038A1 - Ptc 물질을 포함하는 이차전지용 전극을 제조하는 방법 및 이에 의해 제조되는 전극 - Google Patents
Ptc 물질을 포함하는 이차전지용 전극을 제조하는 방법 및 이에 의해 제조되는 전극 Download PDFInfo
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- WO2016099038A1 WO2016099038A1 PCT/KR2015/012461 KR2015012461W WO2016099038A1 WO 2016099038 A1 WO2016099038 A1 WO 2016099038A1 KR 2015012461 W KR2015012461 W KR 2015012461W WO 2016099038 A1 WO2016099038 A1 WO 2016099038A1
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
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- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VROAXDSNYPAOBJ-UHFFFAOYSA-N lithium;oxido(oxo)nickel Chemical group [Li+].[O-][Ni]=O VROAXDSNYPAOBJ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
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- 239000004701 medium-density polyethylene Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 150000004767 nitrides Chemical class 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
- H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
- H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
- H01C17/06573—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the permanent binder
- H01C17/06586—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the permanent binder composed of organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
- H01C7/027—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient consisting of conducting or semi-conducting material dispersed in a non-conductive organic material
-
- 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- 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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
-
- 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
- H01M2200/00—Safety devices for primary or secondary batteries
- H01M2200/10—Temperature sensitive devices
- H01M2200/106—PTC
-
- 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
-
- 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
-
- 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 for secondary batteries comprising a PTC material and to an electrode produced thereby.
- a representative example of an electrochemical device using such electrochemical energy is a secondary battery, and its use area is gradually increasing.
- the secondary battery is classified into a cylindrical battery and a rectangular battery in which the electrode assembly is embedded in a cylindrical or rectangular metal can, and a pouch type battery in which the electrode assembly is embedded in a pouch type case of an aluminum laminate sheet. do.
- the electrode assembly of the anode / separation membrane / cathode structure constituting the secondary battery is largely divided into a jelly-roll type (wound type) and a stack type (lamination type) according to its structure.
- the jelly-roll type electrode assembly is coated with an electrode active material or the like on a metal foil used as a current collector, dried and pressed, cut into bands of a desired width and length, and the membrane is separated using a separator to form a spiral. It is manufactured by winding.
- the jelly-roll type electrode assembly is suitable for cylindrical batteries, but has disadvantages such as peeling problems of electrode active material layers and low space utilization when applied to rectangular or pouch type batteries.
- the stacked electrode assembly has a structure in which a plurality of positive electrode and negative electrode units are sequentially stacked, and it is easy to obtain a rectangular shape.
- a full cell or a cathode (cathode) / separator / cathode (anode) of a basic unit structure of the anode / separator / cathode of a certain unit size A stack / foldable electrode assembly was developed in which a bicell having a basic structure of a separator / anode (cathode) was folded using a continuous membrane film having a long length, and this was applied by Korean Patent Application Publication No. 2001 of the applicant. -82058, 2001-82059, 2001-82060 and the like have been disclosed.
- the electrode assembly when the electrode assembly is penetrated by a sharp needle-like conductor having electrical conductivity, such as a nail, the anode and the cathode are electrically connected by the needle-like conductor, the current flows to the needle-shaped conductor with low resistance. At this time, deformation of the penetrated electrode occurs, and high resistance heat is generated by a current flowing through the contact resistance portion between the positive electrode active material and the negative electrode active material.
- a short circuit occurs due to the contraction of the separator and the contact between the positive electrode and the negative electrode occurs. This short circuit causes a thermal runaway phenomenon, which may act as a main cause of ignition or explosion of the electrode assembly and the secondary battery including the same.
- PTC positive temperature coefficient
- the present invention aims to solve the problems of the prior art as described above and the technical problems that have been requested from the past.
- the first mixture may include a polymer material, conductive particles, and a first binder
- the second mixture may include an electrode active material, a conductive material, and a second binder.
- the first slurry is applied on the current collector, dried, and then dried again after applying the second slurry on the dried first slurry. Method was used. However, in this method, since the drying and the transfer process must be repeated every time one layer is formed, an excessive cost is required for electrode manufacturing.
- the fluidity of the first binder dispersed or dissolved in the solvent is greatly reduced, so that mixing between the first binder contained in the first slurry and the second binder contained in the second slurry is performed.
- the interaction was greatly reduced, and it was difficult to ensure sufficient adhesion between the first mixture layer produced by the drying of the first slurry and the second mixture layer produced by the drying of the second slurry.
- the drying process is performed.
- the cost can be greatly reduced.
- the first binder has sufficient fluidity since the first slurry is dried, so that the first binder and the second binder can partially mix and sufficiently interact at the interface with the second slurry, and as a result, Afterwards, the adhesion between the first mixture layer and the second mixture layer can be significantly improved.
- the binder has a function of preventing the detachment of the polymer material, the conductive particles, the electrode active material, the conductive material, and the like, which may be included in the mixture layer, and the function of securing adhesion to the current collector, and thus, the material included in the mixture layer;
- the first binder and the second binder may have different compositions from each other as appropriately selected according to the type of the current collector.
- the first binder and the second binder may have the same composition, and in this case, since the mixing of the first binder and the second binder becomes easier and the interaction becomes more active, as a result, the first mixture layer and the second binder The adhesive force between 2 mixture layers can be improved further.
- the PTC material exhibits a constant conductivity at the normal operating temperature of the battery, but when the temperature rises, the resistance rapidly increases to block the current.
- the conductive particles are generally mixed with a polymer material having a low electrical conductivity, a low resistance electric passage is formed along the conductive particles. Therefore, in a general situation, although a certain conductivity is exhibited by the electric passage by the conductive particles, when the temperature rises, the distance between the conductive particles increases due to the volume expansion of the polymer material and in some cases the flow of the conductive particles. As the distance between the particles increases, as a result, the resistance of the PTC material increases sharply and the current is cut off.
- the polymer material is not particularly limited as long as the polymer material is low in electrical conductivity and expands in volume when the temperature rises to cut off the electric passage or to block pores, which are passages of ions in the electrode. It may be a polymer.
- the thermoplastic polymer may be a semi-crystalline material, as it may be easier to obtain PTC properties in the semi-crystalline material as compared to amorphous thermoplastics.
- the semi-crystalline thermoplastics may have a crystallinity of at least 5%, in particular at least 10%, and more particularly at least 15%.
- thermoplastic polymer is not particularly limited as long as it meets the above characteristics, but for example, high density polyethylene, linear low density polyethylene, low density polyethylene, medium density polyethylene, maleic anhydride functionalized polyethylene, maleic anhydride functionalized Ethylene acrylics such as elastomers, ethylene copolymers (e.g.
- EXXELOR VA1801 and VA1803 from ExxonMobil ethylene butene copolymers, ethylene octene copolymers, ethylene methyl acrylate, ethylene ethyl acrylate and ethylene butyl acrylate copolymers Copolymers, polyethylene (PE), polypropylene (PP), glycidyl methacrylate modified polyethylene including maleic anhydride functionalized polypropylene, glycidyl methacrylate modified poly Propylene (glycidyl methacrylate modified p olypropylene), polyvinyl chloride (PVC), polyvinyl acetate, polyvinyl acetyl, acrylic resin, syndiotactic polystyrene (sPS), PA6, PA66, PA11, PA12, PA6T, PA9T Polyamide, poly-tetra-fluoroethylene (PTFE), polybutylene terephthalate (PBT), polyphenylene sulf
- the substrate is only one example, and of course, the PTC material may be manufactured using a thermosetting polymer other than the thermoplastic polymer.
- the content of the polymer material may be 1 to 60% by weight, specifically 5 to 50% by weight, based on the total weight of the first mixture.
- the content of the polymer material is less than 1% by weight, it is difficult to effectively block the current because the volume expansion of the PTC material is not large when the temperature is increased.
- the polymer material is not dispersed and present in the form of particles, but aggregates and is present in the form of large agglomerates, thereby deteriorating PTC characteristics.
- the effective operating temperature of the PTC material generated after the drying of the first slurry may be appropriately selected within a range capable of ensuring safety against thermal runaway without disturbing general use of the battery. May range from 140 ° C.
- the content of the binder may be 1 to 60% by weight, specifically 2 to 50% by weight based on the total weight of the first mixture.
- the content of the binder is less than 1% by weight, partial adhesion may not be released due to insufficient adhesive force between the first mixture layer, which is a PTC material layer, and the current collector, or the first mixture layer, and the second mixture layer, which is an active material layer. If a problem may occur, and if it exceeds 60% by weight, the resistance of the electrode is increased, which leads to an increase in the internal resistance of the battery, thereby lowering the overall performance of the battery.
- Such a binder is not particularly limited as long as it can provide sufficient adhesive strength without causing chemical changes, for example, polyvinylidene fluoride, polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropyl Cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluorine rubber, and various It may be at least one selected from the group consisting of copolymers.
- polyvinylidene fluoride polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropyl Cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfon
- the content of the conductive particles may be 1 to 60% by weight, specifically 5 to 50% by weight based on the total weight of the first mixture.
- the content of the conductive particles is less than 1% by weight, the content of the polymer material and the binder are relatively increased to increase the resistance of the electrode, and when the content of the conductive particles is greater than 60% by weight, the content of the binder is relatively decreased to increase the content of the first mixture layer. Adhesion may be reduced.
- Such conductive particles are not particularly limited as long as they have conductivity without causing chemical change, and examples thereof include graphite such as natural graphite and artificial graphite; Carbon blacks such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and summer black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
- graphite such as natural graphite and artificial graphite
- Carbon blacks such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and summer black
- Conductive fibers such as carbon fibers and metal fibers
- Metal powders such as carbon fluoride powder, aluminum powder and nickel powder
- Conductive whiskeys such as zinc oxide and potassium titanate
- Conductive metal oxides such as titanium
- the first slurry and the second slurry in the process (a) and (b) it may be preferable to apply the first slurry thinner than the second slurry in consideration of the capacity of the battery.
- the first slurry in the process (a) may be applied to a thickness of 0.1 to 20 ⁇ m, specifically 0.4 to 3 ⁇ m.
- the second slurry in the process (b) may be applied to a thickness of 5 to 300 ⁇ m, in detail 10 to 200 ⁇ m in a range larger than the thickness of the first slurry.
- the application of the second slurry may be started before the application of the first slurry is completed on the entire surface of the contact.
- the first slurry and the second slurry can be applied on the current collector at about the same time, and the time required for completing the application of the first slurry and the second slurry can be shortened.
- the first slurry is applied to at least a portion of the current collector, and the application of the second slurry can be started within 0.01 seconds to 5 minutes, and when less than 0.01 seconds, the second slurry is applied onto the first slurry. It is difficult to control the process, and it may be difficult to properly generate a PTC material on the current collector after drying, and if it is more than 5 minutes, the thickness of the mixed layer of the first slurry and the second slurry is thin and the first mixture layer after drying It may be difficult to ensure sufficient adhesion between the second mixture layers.
- slurries can be applied in a variety of ways, but for example, by filling the coating material in the concave plate area, the gravure coating to transfer the filled coating material using a roll to roll, and fluidity Die coating may be used, which is applied while flowing the coating material at a constant speed through a slot.
- Such gravure coating has the advantage of applying a thin coating material on the surface, die coating has a relatively thick coating thickness, but the advantage that can be uniformly applied.
- one slurry in the process (a) may be applied using gravure coating or die coating (die coating).
- the thickness of the electrode may be reduced by coating a first slurry that does not include an active material and thus does not contribute to securing battery capacity.
- the first mixture layer formed by drying the first slurry can be prevented from being formed too thin, so that PTC properties necessary for securing the safety of the battery can be obtained, and the first mixture layer, the current collector, and the first mixture layer The adhesive force with a 2nd mixture layer can also be ensured.
- the die coating it is not possible to coat thinner than the gravure coating, but it is possible to apply the first slurry to a thickness of about 1 ⁇ m.
- the second slurry is to be applied to a certain thickness or more for the capacity expression, it may be more appropriate to use a die coating that can be coated thicker than the gravure coating.
- this is not intended to exclude the coating by other methods other than the die coating, it is of course possible to apply by gravure coating.
- the first slurry may be applied using a gravure coating
- the second slurry may be applied using a die coating.
- the electrode is thin and the battery capacity is high, and the safety is improved. Can be obtained.
- the present invention also provides a secondary battery electrode produced by the above production method.
- the secondary battery electrode the current collector of the planar shape; A first mixture layer formed on the current collector and containing a PTC material; A second mixture layer containing an electrode active material; And a mixed layer positioned between the first mixture layer and the second mixture layer, wherein the first mixture layer and the second mixture layer are mixed with each other.
- the mixed layer may be produced by mixing the first slurry and the second slurry and then drying, and may further improve the adhesion between the first mixture layer and the second mixture layer by the mixed layer.
- the present invention also provides an electrode assembly comprising the electrode and the separator.
- the electrode is collectively referred to as an anode and a cathode, hereinafter, other components of the electrode and electrode assembly according to the present invention will be described.
- the positive electrode may be prepared by applying a positive electrode mixture in which a positive electrode active material, a conductive material, and a binder are mixed to a positive electrode current collector, and a filler may be further added to the positive electrode mixture as necessary.
- the positive electrode current collector is generally manufactured to a thickness of 3 ⁇ 300 ⁇ m, and is not particularly limited as long as it has a high conductivity without causing chemical changes in the battery, for example, stainless steel, aluminum, nickel, titanium , And one selected from surface treated with carbon, nickel, titanium, or silver on the surface of aluminum or stainless steel may be used, and in detail, aluminum may be used.
- the current collector may form fine irregularities on its surface to increase the adhesion of the positive electrode active material, and may be in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
- the conductive material is typically added in an amount of 1 to 30% by weight based on the total weight of the positive electrode mixture including the positive electrode active material.
- a conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples thereof include graphite such as natural graphite and artificial graphite; Carbon blacks such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and summer black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
- the binder is a component that assists the bonding of the active material and the conductive material to the current collector, and is generally added in an amount of 1 to 30 wt% based on the total weight of the mixture including the positive electrode active material.
- binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene , Polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers, and the like.
- the filler is optionally used as a component for inhibiting expansion of the positive electrode, and is not particularly limited as long as it is a fibrous material without causing chemical change in the battery.
- the filler include olefinic polymers such as polyethylene and polypropylene; Fibrous materials, such as glass fiber and carbon fiber, are used.
- the negative electrode may be manufactured by applying a negative electrode mixture including a negative electrode active material, a conductive material, and a binder to the negative electrode current collector, and may further include a filler and the like.
- the negative electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery.
- the negative electrode current collector may be formed on the surface of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper, or stainless steel. Surface-treated with carbon, nickel, titanium, silver and the like, aluminum-cadmium alloy and the like can be used.
- fine concavities and convexities may be formed on the surface to enhance the bonding strength of the negative electrode active material, and may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
- the thickness of the negative electrode current collector may be all the same within the range of 3 to 300 ⁇ m, in some cases may have a different value.
- the negative electrode active material may be, for example, carbon such as hardly graphitized carbon or graphite carbon; Li x Fe 2 O 3 (0 ⁇ x ⁇ 1), Li x WO 2 (0 ⁇ x ⁇ 1), Sn x Me 1 - x Me ' y O z (Me: Mn, Fe, Pb, Ge; Me' Metal complex oxides such as Al, B, P, Si, Group 1, Group 2, Group 3 elements of the periodic table, halogen, 0 ⁇ x ⁇ 1; 1 ⁇ y ⁇ 3; 1 ⁇ z ⁇ 8); Lithium metal; Lithium alloys; Silicon-based alloys; Tin-based alloys; SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 O 4 , and metal oxides such as Bi 2
- the separator is interposed between the anode and the cathode, and an insulating thin film having high ion permeability and mechanical strength is used.
- the pore diameter of the separator is generally from 0.01 to 10 micrometers, the thickness is generally from 5 to 30 micrometers.
- olefin polymers such as chemical resistance and hydrophobic polypropylene; Sheets or non-woven fabrics made of glass fibers or polyethylene are used.
- a solid electrolyte such as a polymer
- the solid electrolyte may also serve as a separator.
- the present invention also provides a secondary battery in which the electrode assembly is embedded in a battery case together with an electrolyte solution, wherein the secondary battery is a stack / foldable electrode assembly embedded in a pouch-type battery case of an aluminum laminate sheet containing a non-lithium salt. It may have a structure in which the electrolyte is impregnated.
- the lithium salt-containing nonaqueous electrolyte is composed of a nonaqueous electrolyte and a lithium salt, and the nonaqueous electrolyte may be a nonaqueous organic solvent, an organic solid electrolyte, an inorganic solid electrolyte, or the like, but is not limited thereto.
- non-aqueous organic solvent examples include N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, and gamma Butyl lactone, 1,2-dimethoxy ethane, tetrahydroxyfuran, 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolon, formamide, dimethylformamide, dioxolon, acetonitrile Nitromethane, methyl formate, methyl acetate, triester phosphate, trimethoxy methane, dioxoron derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivatives, Aprotic organic solvents such as tetrahydrofuran derivatives, ethers, methyl pyroionate and ethyl propionate can be used.
- organic solid electrolyte examples include polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphate ester polymers, polyedgetion lysine, polyester sulfides, polyvinyl alcohol, polyvinylidene fluoride, and ions. Polymerizers containing a sex dissociation group and the like can be used.
- Examples of the inorganic solid electrolyte include Li 3 N, LiI, Li 5 NI 2 , Li 3 N-LiI-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3 , Li 4 SiO 4 , Nitrides, halides, sulfates and the like of Li, such as Li 4 SiO 4 -LiI-LiOH, Li 3 PO 4 -Li 2 S-SiS 2 , and the like, may be used.
- the lithium salt is a good material to be dissolved in the nonaqueous electrolyte, and for example, LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li, (CF 3 SO 2 ) 2 NLi, chloroborane lithium, lower aliphatic lithium carbonate, lithium tetraphenylborate, imide and the like can be used.
- nonaqueous electrolytes include pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, for the purpose of improving charge and discharge characteristics, flame retardancy, and the like.
- Nitrobenzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium salts, pyrroles, 2-methoxy ethanol, aluminum trichloride and the like may be added. have.
- a halogen-containing solvent such as carbon tetrachloride or ethylene trifluoride may be further included, and carbon dioxide gas may be further included to improve high temperature storage characteristics, and FEC (Fluoro-Ethylene) may be further included. Carbonate), PRS (Propene sultone) may be further included.
- lithium salts such as LiPF 6 , LiClO 4 , LiBF 4 , LiN (SO 2 CF 3 ) 2, and the like, may be prepared by cyclic carbonate of EC or PC, which is a highly dielectric solvent, and DEC, DMC, or EMC, which are low viscosity solvents.
- Lithium salt-containing nonaqueous electrolyte can be prepared by adding to a mixed solvent of linear carbonate.
- the present invention also provides a battery pack including the secondary battery as a unit cell, and a device including the battery pack as a power source.
- Such devices may be, for example, mobile phones, portable computers, smartphones, smart pads, tablet PCs, netbooks, wearable electronics, electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, and power storage devices.
- the present invention is not limited thereto.
- Such a lithium secondary battery, a structure of a battery pack including the same as a unit cell, and a method of manufacturing a device including the battery pack as a power source are well known in the art, and thus a detailed description thereof will be omitted.
- FIG. 1 is a schematic diagram showing an electrode for a secondary battery including a PTC material according to an embodiment of the present invention.
- FIG. 1 is a schematic diagram schematically showing an electrode for a secondary battery including a PTC material according to an embodiment of the present invention.
- the electrode 100 includes a current collector 110, a first mixture layer 120, and a second mixture layer 130.
- a first mixture layer 120 including a PTC material is formed on an upper surface of the current collector 110, and a second mixture layer 130 including an electrode active material is formed on an upper surface of the first mixture layer 120.
- the electrode active material included in the second mixture layer 130 may be a positive electrode active material or a negative electrode active material, and an appropriate current collector 110 may be selected according to the electrode active material.
- the interface between the first mixture layer 120 and the second mixture layer 130 is represented as a plane, but this is only for schematically representing the structure of the electrode 100, and in fact, an undried state. Since the second slurry is prepared by applying the second slurry on the first slurry, the section in which the first slurry and the second slurry are mixed may exist at these interfaces, and thus, it may be difficult to clearly determine the interface between them. In addition, since there is a section in which the first slurry and the second slurry are partially mixed, the first mixture layer 120 and the second mixture are dried after the slurry is dried as compared with the electrode manufactured by the conventional electrode manufacturing method. There is an effect that the adhesion between the layers 130 is further improved.
- the thickness of the first mixture layer 120 including the PTC material applied to the current collector 110 is relatively thinner than that of the second mixture layer 130 including the electrode active material, which is the first mixture layer. This is to secure the capacity of the battery while ensuring safety by the PTC material included in 120.
- the electrons may pass through the second mixture layer 130 via the first mixture layer 120. Since the current cannot be moved between the current collectors 110, current is cut off, and as a result, thermal runaway of the battery can be prevented.
- an effective operating temperature of the PTC material included in the first mixture layer 120 may be 80 to 140 ° C.
- the electrode 100 of FIG. 1 shows the cross-sectional electrode in which the 1st mixture layer 120 and the 2nd mixture layer 130 are formed only in the upper surface of the electrical power collector 110, it uses the manufacturing method of this invention.
- the mixture layer including the PTC material and the mixture layer including the electrode active material are sequentially formed on the lower surface of the current collector 110, and both surfaces of the current collector 110 are symmetrical with respect to the top and bottom surfaces thereof.
- the electrode can also be manufactured.
- the method for manufacturing a secondary battery electrode according to the present invention including the step of applying a second slurry on the first slurry in an undried state, a reasonable level when producing an electrode containing a PTC material As a result, the electrode manufacturing cost can be reduced, and the adhesion between the PTC material layer and the electrode active material layer can be secured.
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Abstract
Description
Claims (22)
- PTC (Positive Temperature Coefficient) 물질을 포함하는 이차전지용 전극을 제조하는 방법으로서,(a) 평면 형상의 집전체의 일면에 건조 후 PTC 물질이 생성될 수 있도록, 제 1 합제 및 용매가 혼합된 제 1 슬러리를 도포하는 과정;(b) 상기 집전체에 도포된 미건조 상태의 제 1 슬러리 상에, 전극 활물질을 포함하는 제 2 합제 및 용매가 혼합된 제 2 슬러리를 도포하는 과정; 및(c) 상기 집전체에 도포된 제 1 슬러리 및 제 2 슬러리를 건조하는 과정;을 포함하는 것을 특징으로 하는 전극의 제조 방법.
- 제 1 항에 있어서, 상기 제 1 합제는 고분자 재료, 도전성 입자들, 및 제 1 바인더를 포함하는 것을 특징으로 하는 전극의 제조 방법.
- 제 1 항에 있어서, 상기 제 2 합제는 전극 활물질, 도전재, 및 제 2 바인더를 포함하는 것을 특징으로 하는 전극의 제조 방법.
- 제 2 항 또는 제 3 항에 있어서, 상기 제 1 바인더와 제 2 바인더는 조성이 서로 상이한 것을 특징으로 하는 전극의 제조 방법.
- 제 2 항 또는 제 3 항에 있어서, 상기 제 1 바인더와 제 2 바인더는 조성이 서로 동일한 것을 특징으로 하는 전극의 제조 방법.
- 제 2 항에 있어서, 상기 고분자 재료의 함량은 제 1 합제의 전체 중량을 기준으로 1 내지 60 중량%인 것을 특징으로 하는 전극의 제조 방법.
- 제 2 항에 있어서, 상기 도전성 입자들의 함량은 제 1 합제의 전체 중량을 기준으로 1 내지 60 중량%인 것을 특징으로 하는 전극의 제조 방법.
- 제 1 항에 있어서, 상기 제 1 슬러리의 건조 후 생성되는 PTC 물질의 유효 작동 온도는 80 내지 140℃ 인 것을 특징으로 하는 전극의 제조 방법.
- 제 2 항에 있어서, 상기 바인더의 함량은 제 1 합제의 전체 중량을 기준으로 1 내지 60 중량%인 것을 특징으로 하는 전극의 제조 방법.
- 제 1 항에 있어서, 상기 과정 (a)에서 제 1 슬러리는 그라비아 코팅(gravure coating) 또는 다이 코팅(die coating)을 이용하여 도포되는 것을 특징으로 하는 전극의 제조 방법.
- 제 1 항에 있어서, 상기 과정 (b)에서 제 2 슬러리는 다이 코팅을 이용하여 도포되는 것을 특징으로 하는 전극의 제조 방법.
- 제 1 항에 있어서, 상기 과정 (a)에서 제 1 슬러리는 0.1 내지 20 ㎛ 두께로 도포되는 것을 특징으로 하는 전극의 제조 방법.
- 제 1 항에 있어서, 상기 과정 (b)에서 제 2 슬러리는 제 1 슬러리의 두께보다 큰 범위에서 5 내지 300 ㎛ 두께로 도포되는 것을 특징으로 하는 전극의 제조 방법.
- 제 1 항에 있어서, 상기 과정(b)에서 접전체의 일면 전체에 제 1 슬러리의 도포가 완료되기 전에 제 2 슬러리의 도포를 개시하는 것을 특징으로 하는 전극의 제조 방법.
- 제 1 항에 있어서, 상기 과정(b)에서 집전체의 적어도 일부에 제 1 슬러리가 도포되고 0.01 초 내지 5 분 내에 제 2 슬러리의 도포를 개시하는 것을 특징으로 하는 전극의 제조 방법.
- 제 1 항에 따른 제조 방법에 의해 제조 되는 것을 특징으로 하는 이차전지용 전극.
- 제 16 항에 있어서, 상기 이차전지용 전극은,평면 형상의 집전체;상기 집전체 상에 형성되어 있고, PTC 물질을 포함하는 제 1 합제층;전극 활물질을 포함하는 제 2 합제층; 및상기 제 1 합제층과 제 2 합제층 사이에 위치하며, 제 1 합제층과 제 2 합제층이 혼합되어 있는 혼합층;을 포함하고 있는 것을 특징으로 하는 이차전지용 전극.
- 제 16 항에 따른 이차전지용 전극을 포함하는 것을 특징으로 하는 전극조립체.
- 제 18 항에 따른 전극조립체가 전해액과 함께 전지케이스에 내장되어있는 것을 특징으로 하는 이차전지.
- 제 19 항에 따른 이차전지를 단위전지로서 포함하는 것을 특징으로 하는 전지팩.
- 제 20 항에 따른 전지팩을 전원으로서 포함하고 있는 것을 특징으로 하는 디바이스.
- 제 21 항에 있어서, 상기 디바이스는 휴대폰, 휴대용 컴퓨터, 스마트폰, 스마트 패드, 태블릿 PC, 넷북, 웨어러블 전자기기, 전기자동차, 하이브리드 전기자동차, 플러그-인 하이브리드 전기자동차 및 전력저장 장치로 이루어진 군에서 선택되는 것을 특징으로 하는 디바이스.
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US15/510,070 US10608289B2 (en) | 2014-12-16 | 2015-11-19 | Method of manufacturing secondary battery electrode containing PTC material and electrode manufactured thereby |
JP2017513796A JP6819941B2 (ja) | 2014-12-16 | 2015-11-19 | Ptc物質を含む二次電池用電極を製造する方法及びそれにより製造される電極 |
CN201580050399.7A CN107004858B (zh) | 2014-12-16 | 2015-11-19 | 含有ptc材料的二次电池电极的制造方法和由此方法制造的电极 |
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US20170309970A1 (en) | 2017-10-26 |
JP6819941B2 (ja) | 2021-01-27 |
KR101709569B1 (ko) | 2017-02-23 |
US10608289B2 (en) | 2020-03-31 |
CN107004858A (zh) | 2017-08-01 |
CN107004858B (zh) | 2020-09-18 |
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