WO2011070661A1 - 電池用電極の製造方法 - Google Patents

電池用電極の製造方法 Download PDF

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Publication number
WO2011070661A1
WO2011070661A1 PCT/JP2009/070649 JP2009070649W WO2011070661A1 WO 2011070661 A1 WO2011070661 A1 WO 2011070661A1 JP 2009070649 W JP2009070649 W JP 2009070649W WO 2011070661 A1 WO2011070661 A1 WO 2011070661A1
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Prior art keywords
layer
binder
active material
binder solution
current collector
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PCT/JP2009/070649
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English (en)
French (fr)
Japanese (ja)
Inventor
信之 山崎
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トヨタ自動車株式会社
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Application filed by トヨタ自動車株式会社 filed Critical トヨタ自動車株式会社
Priority to CN200980162820.8A priority Critical patent/CN102656723B/zh
Priority to JP2011545020A priority patent/JP5397711B2/ja
Priority to PCT/JP2009/070649 priority patent/WO2011070661A1/ja
Priority to KR1020127017772A priority patent/KR101389596B1/ko
Priority to US13/513,865 priority patent/US8877386B2/en
Publication of WO2011070661A1 publication Critical patent/WO2011070661A1/ja

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L50/00—Electric propulsion with power supplied within the vehicle
    • B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a method of manufacturing a battery electrode, and more particularly to a method of manufacturing a battery electrode having a configuration in which an electrode mixture layer containing an electrode active material is held by a current collector.
  • a lithium secondary battery that is lightweight and has a high energy density is expected to be preferably used as a high-output power source for mounting on a vehicle.
  • an electrode having a configuration in which a material (electrode active material) capable of reversibly occluding and releasing lithium ions is held in a conductive member (electrode current collector) is used.
  • an oxide containing lithium and one or more transition metal elements as constituent metal elements is exemplified.
  • a typical example of an electrode current collector (positive electrode current collector) used for the positive electrode is a sheet-like or foil-like member mainly composed of aluminum or an aluminum alloy.
  • a powder of a positive electrode active material and a binder (binder) are dispersed in an appropriate medium.
  • a paste-form or slurry-form active material layer forming material (hereinafter referred to as an active material layer forming paste) is applied to a positive electrode current collector, and this is passed through a hot air dryer and dried to obtain a positive electrode active material.
  • the method of forming the layer (positive electrode active material layer) containing is mentioned.
  • the binder contained in the positive electrode active material layer is made of, for example, a polymer material, and plays a role of binding the positive electrode active materials contained in the positive electrode active material layer or between the positive electrode active material layer and the positive electrode current collector.
  • Patent document 1 is mentioned as a prior art regarding this kind of electrode manufacture.
  • a paste for forming a mixture layer containing an active material and a binder is applied to a current collector and dried by applying hot air, and convection occurs during drying, and the vicinity of the current collector
  • the binder in the surface of the paste coating will float on the surface layer (opposite the current collector), reducing the amount of binder near the current collector, resulting in improved adhesion (adhesive strength) between the current collector and the composite layer. There is a problem of lowering.
  • Patent Document 1 describes a technique in which a binder layer containing a binder is provided between a current collector and an active material layer in order to improve adhesion between the current collector and the composite material layer.
  • a binder layer is coated on the surface of the current collector, and an active material layer is coated on the binder layer while the coated binder layer is in a wet state. The If this method is used, adhesion between the binder layer and the active material layer becomes strong, and delamination of these layers can be prevented.
  • the present invention has been made in view of the above points, and its main object is to provide a current collector and an active material in a battery electrode having a structure in which a binder layer and an active material layer are sequentially laminated on the current collector. It is providing the manufacturing method of the electrode for batteries which can reduce the interface resistance of a layer.
  • a method for manufacturing a battery electrode having a structure in which a binder layer containing a binder and an active material layer containing an active material are sequentially laminated on a current collector includes a step of mixing microbubbles into a binder solution containing a binder, a step of forming the binder solution layer by applying the bubbled binder solution to a current collector, and an active material from above the binder solution layer.
  • the microbubble referred to in the present specification is a fine bubble having a diameter of a micrometer order or less (that is, a nanoorder having a diameter of 1 ⁇ m or less), for example, 50 ⁇ m or less (particularly preferable).
  • Microbubbles are very fine bubbles and generally have a charging effect (typically the surface of the microbubbles is negatively charged), so that the growth of the bubbles connected to each other is suppressed. The floating speed is slow and therefore stays in the liquid for a long time.
  • the microbubbles are mixed in the binder solution and then applied to the current collector. Therefore, the microbubbles are in the binder solution layer (that is, the wet binder layer) until it is dried thereafter. Continue to stay inside. When the binder solution layer is dried in this state, the microbubbles escape to the outside while maintaining the internal space, so that many traces (holes) of microbubbles are formed in the binder layer obtained after drying. A conductive path between the current collector and the active material layer is secured through the traces (holes) of the microbubbles (typically through the active material or conductive material filled in the holes), and the current collection The interface resistance between the body and the active material layer can be lowered.
  • the adhesion between the current collector and the active material layer is suppressed by the binder layer while the increase in the interface resistance between the current collector and the active material layer is suppressed by the traces (holes) of the microbubbles.
  • Adhesive strength can be increased, and a high-performance battery electrode having both current collecting performance and adhesion can be produced.
  • bubbles smaller than the thickness of the binder solution layer are mixed as the microbubbles.
  • the binder solution layer is formed to a thickness of 5 ⁇ m to 100 ⁇ m.
  • the binder solution layer is formed to have a thickness of approximately 10 ⁇ m, it is preferable to incorporate bubbles having a diameter of less than 10 ⁇ m (typically 1 ⁇ m to 10 ⁇ m, and particularly preferably 2 ⁇ m to 10 ⁇ m).
  • the lower limit of the bubble diameter is not particularly limited, but is about 1 ⁇ m, for example. If the diameter is too small, the microbubbles gradually shrink in the binder solution layer and finally dissolve (before the binder solution layer is dried), and traces of voids of appropriate size (voids) ) May not be formed. Accordingly, it is preferable that the bubble diameter of the microbubbles is approximately 1 ⁇ m or more (preferably 5 ⁇ m or more) and less than the thickness of the binder solution layer to be formed (for example, less than 10 ⁇ m).
  • bubbles of 1 ⁇ m to 20 ⁇ m, particularly 2 ⁇ m to 10 ⁇ m are preferable in that they can be stably formed with desired traces (holes) in the binder layer because they have a low floating speed in the liquid and exist for a long time.
  • bubbles composed of a gas having a specific heat smaller than that of the solvent of the binder solution are mixed as the microbubbles.
  • water specific heat 4.271 J / g ⁇ K
  • bubbles composed of a gas having a specific heat smaller than that of water are mixed.
  • bubbles composed of Ar gas specific heat 0.523 J / g ⁇ K
  • the binder solution layer can be more easily dried and the drying efficiency (and thus the productivity of the electrode) can be improved.
  • the said binder solution can contain other binder layer formation components other than the said binder and microbubble as needed.
  • a material is a conductive material.
  • the conductive material carbon-based materials such as carbon black, such as acetylene black (AB), or carbon fiber are preferably used.
  • conductive metal powder such as nickel powder may be used.
  • the microbubbles are charged with a predetermined polarity
  • the binder solution contains a conductive material that can be charged with a polarity opposite to the polarity of the microbubbles.
  • the conductive material is preferably charged positively.
  • the conductive material gathers around the microbubble due to the electric attractive force (electrostatic attractive force).
  • the conductive material is selectively disposed in traces (holes) of microbubbles generated by drying. This can effectively reduce the interface resistance between the current collector and the active material layer.
  • a battery for example, a lithium secondary battery constructed using the electrode obtained by any one of the methods disclosed herein.
  • a battery exhibits excellent battery performance because it is constructed using at least one of the electrodes.
  • a battery satisfying at least one of excellent output characteristics, high cycle durability, and good productivity can be provided.
  • Such a battery is suitable as a battery mounted on a vehicle such as an automobile. Therefore, according to the present invention, there is provided a vehicle including any of the batteries disclosed herein (which may be in the form of an assembled battery in which a plurality of batteries are connected).
  • the battery is a lithium secondary battery (typically a lithium ion battery), and the lithium secondary battery is used as a power source (typically a hybrid vehicle or an electric vehicle).
  • a vehicle for example, an automobile
  • a power source is preferable.
  • FIG. 1 is a cross-sectional view schematically showing a positive electrode according to an embodiment of the present invention.
  • FIG. 2 is a diagram schematically showing a binder solution according to an embodiment of the present invention.
  • FIG. 3 is a cross-sectional view schematically showing a manufacturing process of the positive electrode according to one embodiment of the present invention.
  • FIG. 4 is a cross-sectional view schematically showing a manufacturing process of the positive electrode according to one embodiment of the present invention.
  • FIG. 5 is a cross-sectional view schematically showing a manufacturing process of the positive electrode according to one embodiment of the present invention.
  • FIG. 6 is a diagram schematically showing a battery according to an embodiment of the present invention.
  • FIG. 7 is a side view of a vehicle equipped with a battery according to an embodiment of the present invention.
  • the positive electrode (positive electrode sheet) for a lithium secondary battery (typically a lithium ion battery) will be used as an example, and the method for manufacturing a battery electrode according to this embodiment will be described below. Will be described.
  • a binder layer 20 including a binder and a positive electrode active material layer 30 including a positive electrode active material 32 are sequentially stacked on the positive electrode current collector 10. This is a method for manufacturing a battery positive electrode 40 having a configuration.
  • a binder solution 50 in which a binder (not shown) is dispersed in a predetermined solvent (for example, water) is prepared, and microbubbles 52 are mixed into the binder solution. .
  • a binder solution 50 containing bubbles 52 is applied to the current collector 10 to form a binder solution layer (that is, a wet binder layer) 56.
  • the binder solution layer 56 and the paste layer (that is, the wet active material layer) are applied.
  • 36 on the positive electrode current collector 10 and, as shown in FIG. 5, by drying the deposited binder solution layer 56 and the paste layer 36 together, a binder layer is formed on the positive electrode current collector 10. 20 and the positive electrode 40 in which the positive electrode active material layer 30 is formed are obtained.
  • the microbubble 52 is a fine bubble having a diameter of a micrometer order or less (that is, a nanoorder having a diameter of 1 ⁇ m or less), for example, approximately 50 ⁇ m or less (particularly preferably 10 ⁇ m or less). ).
  • the microbubbles 52 are very fine bubbles and generally have a charging action (typically, the surface of the bubble 52 is negatively charged as shown in FIG. 2), so that the bubbles may be connected and grow. It is suppressed and the floating speed in the liquid is slow, so it stays in the liquid for a long time.
  • the microbubbles 52 are mixed in the binder solution 50 and then applied to the current collector 10.
  • the bubble 52 continues to stay in the binder solution layer 56.
  • the binder solution layer 56 is dried in this state, the microbubbles 52 escape to the outside while maintaining the internal space. Therefore, as shown in FIG. 5, traces of microbubbles (empty spaces) are formed in the binder layer 20 obtained after the drying. Many holes 22 are formed. Conduction between the current collector 10 and the active material layer 30 through the traces (holes) 22 of the microbubbles (typically via an active material filled in the holes 22 or a conductive material 54 described later).
  • the binder layer 20 suppresses the increase in the interface resistance between the current collector 10 and the active material layer 30 by the microbubble traces (holes) 22, while Adhesiveness (adhesive strength) with the material layer 30 can be increased, and a high-performance battery electrode 40 that achieves both current collecting performance and adhesiveness can be manufactured.
  • a binder solution 50 containing a binder is prepared, and microbubbles 52 are mixed into the binder solution 50.
  • an aqueous solvent As the solvent for the binder solution, it is preferable to use an aqueous solvent from various viewpoints such as reduction of environmental load, reduction of material cost, simplification of equipment, reduction of waste, and improvement of handleability.
  • aqueous solvent water or a mixed solvent mainly composed of water is preferably used.
  • a solvent component other than water constituting such a mixed solvent one or more organic solvents (lower alcohol, lower ketone, etc.) that can be uniformly mixed with water can be appropriately selected and used.
  • an aqueous solvent in which 80% by mass or more (more preferably 90% by mass or more, more preferably 95% by mass or more) of the aqueous solvent is water.
  • a particularly preferred example is an aqueous solvent substantially consisting of water.
  • the solvent is not limited to an aqueous solvent and may be a non-aqueous solvent.
  • the non-aqueous solvent for example, N-methylpyrrolidone (NMP) can be used.
  • the gas constituting the microbubble is not particularly limited as long as it can be stably retained in the solvent of the binder solution.
  • argon (Ar) gas carbonic acid (CO 2 ) gas, nitrogen (N 2 ) gas, air, or the like can be used.
  • Ar gas is Ar gas.
  • the above-described constituent gases may be used alone or in combination of two or more.
  • bubbles composed of a gas having a specific heat smaller than that of the solvent of the binder solution are mixed as the microbubbles.
  • water specific heat 4.271 J / g ⁇ K
  • bubbles composed of a gas having a specific heat smaller than that of water are mixed.
  • bubbles composed of Ar gas specific heat 0.523 J / g ⁇ K
  • the binder solution layer 56 can be easily dried, and the drying efficiency (and thus the productivity of the electrode) can be improved.
  • the bubble diameter (diameter) of the microbubbles is not particularly limited, but it is preferable to incorporate bubbles smaller than the thickness of the binder solution layer 56.
  • the binder solution layer is formed to have a thickness of approximately 10 ⁇ m, it is preferable to incorporate bubbles having a diameter of less than 10 ⁇ m (typically 1 ⁇ m to 10 ⁇ m, and particularly preferably 2 ⁇ m to 10 ⁇ m).
  • the bubbles having a diameter exceeding the thickness of the binder solution layer 56 to be formed are used, the bubbles easily escape from the binder solution layer 56, and an appropriate trace (conductivity between the current collector and the active material layer) is formed in the binder layer 20. In some cases, it is not possible to form holes 22 having a size suitable for securing a pass.
  • the lower limit of the bubble diameter is not particularly limited, but is about 1 ⁇ m, for example. If the diameter is too small, the microbubbles are gradually reduced in the binder solution layer and finally dissolved (before the binder solution layer is dried), and a trace (empty) of an appropriate size is formed in the binder layer 20. Hole) 22 may not be formed. Therefore, the bubble diameter of the microbubbles is preferably about 1 ⁇ m or more (preferably 5 ⁇ m or more) and less than the thickness of the binder solution layer to be formed (for example, 10 ⁇ m or less).
  • bubbles of 1 ⁇ m to 20 ⁇ m, particularly 2 ⁇ m to 10 ⁇ m are preferable in that they can be stably formed with desired traces (holes) in the binder layer because they have a low floating speed in the liquid and exist for a long time.
  • the total volume of bubbles contained in 1 cm 3 of the binder solution mixed with microbubbles is 0.1 cm 3 to 0.9 cm when the solution is applied to the current collector. About 3 , preferably about 0.6 cm 3 to 0.8 cm 3 . If the volume is too small than this range, the amount of traces (vacancies) in the binder layer may be too small to form an appropriate conductive path between the current collector and the active material layer. If the volume is too large, the amount of traces (vacancies) in the binder layer increases so that appropriate adhesion (adhesive strength) between the current collector and the active material layer may not be obtained. Typically, 10% by volume or more (preferably 50% by volume or more) of the above-mentioned bubbles may be contained in the solution as microbubbles. Substantially all of the bubbles contained in the solution may be microbubbles.
  • the operation for mixing such microbubbles into the binder solution 50 is not particularly limited. For example, it may be performed by mixing a predetermined amount of microbubbles into the binder solution using an appropriate bubble generator (for example, a bubble generator using a gas-liquid shearing method).
  • an appropriate bubble generator for example, a bubble generator using a gas-liquid shearing method.
  • the binder is not particularly limited as long as it is the same as the binder (binder) used in the conventional positive electrode for a lithium secondary battery.
  • a water-soluble or water-dispersible polymer such as styrene butadiene rubber (SBR), carboxymethyl cellulose (CMC), polytetrafluoroethylene (PTFE), polyethylene (PE), polyacrylic acid (PAA) can be used.
  • SBR styrene butadiene rubber
  • CMC carboxymethyl cellulose
  • PTFE polytetrafluoroethylene
  • PE polyethylene
  • PAA polyacrylic acid
  • an organic solvent-based polymer such as polyvinylidene fluoride (PVDF) or polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) can be used.
  • the said binder solution can contain other binder layer formation components other than the said binder and microbubble as needed.
  • a material is a conductive material.
  • carbon-based materials such as carbon black, such as acetylene black (AB), or carbon fiber are preferably used.
  • conductive metal powder such as nickel powder may be used.
  • the microbubbles 52 are charged with a predetermined polarity
  • the binder solution 50 contains a conductive material 54 that can be charged with a polarity opposite to the polarity of the microbubbles 52.
  • the surface of the microbubble 52 is negatively charged.
  • the conductive material 54 is preferably charged positively.
  • the conductive material 54 gathers around the microbubbles 42 due to an electric attractive force (electrostatic attractive force). Therefore, as shown in FIG. 5, the conductive material 54 is selectively disposed in the traces (holes) 22 of the microbubbles generated by the drying. This can effectively reduce the interface resistance between the current collector and the active material layer.
  • the method for charging the conductive material 54 to positive is not particularly limited.
  • a conductive agent having a property that the material itself can be positively charged from the beginning can be used.
  • examples of such a conductive agent include carbon-based materials such as carbon black (for example, acetylene black) and carbon fiber.
  • a special treatment may be performed such that the conductive material is positively charged.
  • a contact charging method in which a charging member to which a voltage is applied is brought into contact with a conductive material can be adopted.
  • the magnitude of the negative potential of the microbubble is usually about ⁇ 10 mV to ⁇ 50 mV (eg, ⁇ 30 mV).
  • the magnitude of the positive potential of the conductive material is preferably about 10 mV to 50 mV, and usually about 20 mV to 40 mV.
  • the magnitude of the potential can be grasped by, for example, a zeta electrometer.
  • the solid content of the binder solution 50 is preferably about 2% by mass or more, and more preferably about 5% by mass to 40% by mass. Further, the ratio of the binder contained in the solid content of the binder solution 50 is preferably about 15% by mass or more, and more preferably about 15% by mass to 30% by mass. The ratio of the conductive material contained in the solid content of the binder solution 50 is preferably about 70% by mass or more, and more preferably about 70% by mass to 85% by mass.
  • the binder solution layer 56 is then formed by applying (typically applying) the binder solution to the current collector 10 as shown in FIG.
  • a general fluid application technique such as a printing method (ink jet method, letterpress printing, gravure printing, screen printing, etc.) or a dispenser method may be employed. it can.
  • a method of applying the binder solution 50 to the current collector 10 includes a method of applying the binder solution in a layered manner on the surface of the current collector using a gravure printing method. Thereby, the binder solution layer 56 having a uniform thickness can be formed.
  • the thickness of the binder solution layer can be usually 2 ⁇ m to 100 ⁇ m (for example, 5 ⁇ m to 100 ⁇ m), for example, 2 ⁇ m to 20 ⁇ m (typically about 5 ⁇ m to 20 ⁇ m, for example, about 10 ⁇ m).
  • binder solution layer 56 After forming the binder solution layer 56 in this way, next, as shown in FIG. 4, by applying an active material layer forming paste containing an active material from above the binder solution layer 56, a binder solution layer is formed. 56 and a paste layer (wet active material layer) 36 are deposited on the current collector 10.
  • the active material layer forming paste is obtained by mixing the positive electrode active material (typically powder) 32 and other positive electrode active material layer forming components used as necessary in an appropriate solvent. Can be prepared.
  • the positive electrode active material (typically powder) 32 is not particularly limited as long as it is the same as that used for a typical lithium ion secondary battery.
  • the positive electrode active material 32 used for the positive electrode lithium and one or two of lithium nickel oxide (LiNiO 2 ), lithium cobalt oxide (LiCoO 2 ), lithium manganese oxide (LiMn 2 O 4 ), and the like are used.
  • Examples thereof include a positive electrode active material having as its main component an oxide (lithium-containing composite oxide) containing at least one kind of transition metal element as a constituent metal element.
  • a lithium-containing composite oxide for example, a lithium-containing composite oxide powder prepared by a conventionally known method can be used as it is.
  • lithium-containing composite oxide powder substantially composed of secondary particles having an average particle diameter in the range of about 1 ⁇ m to 25 ⁇ m can be preferably used as the positive electrode active material.
  • the solvent used for the active material layer forming paste include water or a mixed solvent mainly composed of water (aqueous solvent).
  • a solvent other than water constituting such a mixed solvent one or more organic solvents (lower alcohol, lower ketone, etc.) that can be uniformly mixed with water can be appropriately selected and used.
  • the solvent is not limited to an aqueous solvent, and may be a non-aqueous solvent.
  • NMP N-methylpyrrolidone
  • the active material layer forming paste may contain one or two or more kinds of materials that can be used as a constituent component of a positive electrode active material layer in a general lithium secondary battery, if necessary.
  • An example of such a material is a conductive material.
  • the conductive material may be the same material as the conductive material 54 included in the binder layer 30 or may be a different material.
  • examples of the material that can be used as a component of the positive electrode active material layer include various polymer materials that can function as a binder (binder) of the above constituent materials. This binder may be the same material as the binder included in the binder layer 30 or may be a different material.
  • the operation of applying (typically applying) such a paste for forming an active material layer to the current collector 10 uses the current collector having the binder solution layer 56 formed on the surface as described above. Except for the above, it can be carried out in the same manner as the conventional production of a positive electrode for a lithium secondary battery. For example, by applying a predetermined amount of the active material layer forming paste 36 onto the current collector 10 from above the binder solution layer 56 using a suitable coating device (die coater or the like), the paste layer 36 Can be formed.
  • a suitable coating device die coater or the like
  • the binder solution layer 56 and the paste layer 36 are deposited on the current collector in this way, the deposited binder solution layer 56 and the paste layer 36 are then dried together, as shown in FIG.
  • the positive electrode 40 in which the binder layer 20 and the active material layer 30 are sequentially formed on the electric body 10 is obtained.
  • the method for drying the binder solution layer and the paste layer can be performed in the same manner as the conventional method for producing a positive electrode for a lithium secondary battery.
  • the binder solution layer and the paste layer can be dried by passing the current collector 10 through a suitable drying furnace and applying hot air from both sides of the current collector 10.
  • the solvent in the paste layer is 3.0 ml / s or more per 1 m 2 of liquid surface area (that is, 3.0 ml / s ⁇ m 2 or more), for example 3 .2ml / s ⁇ m 2 ⁇ 5.0ml / s ⁇ m 2 ( preferably 4.0ml / s ⁇ m 2 ⁇ 5.0ml / s ⁇ m 2) can be volatilized at a rate of.
  • the solvent in the paste layer is 3.0 ml / s ⁇ m 2 or more (preferably 4.0 ml / s ⁇ m 2 or more), and the productivity is dramatically improved.
  • the battery positive electrode 40 having a configuration in which the binder layer 20 including the binder and the active material layer 30 including the positive electrode active material 32 are sequentially stacked on the positive electrode current collector 10 can be manufactured.
  • an appropriate press process for example, various well-known press methods, such as a roll press method and a flat plate press method, can be used
  • the thickness and density can also be adjusted as appropriate.
  • the electrode 40 thus obtained has a low interface resistance between the current collector 10 and the active material layer 30 and excellent adhesion between the current collector 10 and the active material layer 30. It can preferably be used as a component of a battery of the form or a component (for example, positive electrode) of an electrode body incorporated in the battery.
  • a positive electrode obtained by any of the methods disclosed herein, a negative electrode (which may be a negative electrode produced by applying the present invention), an electrolyte disposed between the positive and negative electrodes, Can be preferably used as a component of a lithium secondary battery including a separator that separates the positive and negative electrodes (can be omitted in a battery using a solid or gel electrolyte).
  • Structure for example, metal casing or laminate film structure
  • the battery constructed in this manner includes the electrode 40 that has excellent adhesion between the current collector 10 and the active material layer 30 and has low interface resistance between the current collector 10 and the active material layer 30. It shows excellent battery performance. For example, by constructing a battery using the above electrode, a battery satisfying at least one of excellent output characteristics, high cycle durability, and good productivity can be provided.
  • a positive electrode (positive electrode sheet) 40 manufactured by applying the above-described method is used as the positive electrode (positive electrode sheet) 40.
  • the lithium secondary battery 100 includes a case 82 made of metal (a resin or a laminate film is also suitable).
  • the case (outer container) 82 includes a flat cuboid case main body 84 having an open upper end, and a lid 86 that closes the opening.
  • a positive electrode terminal 74 that is electrically connected to the positive electrode 40 of the electrode body 80 and a negative electrode terminal 72 that is electrically connected to the negative electrode 70 of the electrode body are provided.
  • a long sheet-like positive electrode (positive electrode sheet) 40 and a long sheet-like negative electrode (negative electrode sheet) 70 are laminated together with a total of two long sheet-like separators (separator sheets) 76.
  • a flat wound electrode body 80 produced by winding and then crushing the resulting wound body from the side direction and kidnapping is housed.
  • the positive electrode sheet 40 has a configuration in which the negative electrode active material layer 30 mainly composed of the positive electrode active material is provided on both surfaces of the long sheet-like positive electrode current collector 10 via the binder layer 20 ( (See FIG. 1).
  • the positive electrode current collector an aluminum foil or other metal foil suitable for the positive electrode is preferably used.
  • the negative electrode sheet 70 has a configuration in which a negative electrode active material layer containing a negative electrode active material as a main component is provided on both surfaces of a long sheet-like negative electrode current collector.
  • the electrode manufacturing method disclosed here can be applied to manufacture of both the positive electrode and the negative electrode.
  • the negative electrode sheet 70 may be a negative electrode sheet 70 manufactured by applying the above-described method using the bubble-containing binder solution 50. At one end in the width direction of these electrode sheets 30, 70, an electrode active material layer non-formed portion where the electrode active material layer is not provided on any surface is formed.
  • the positive electrode sheet 40 and the negative electrode active material layer non-formed part of the positive electrode sheet 40 and the negative electrode active material layer non-formed part of the negative electrode sheet 70 protrude from both sides in the width direction of the separator sheet 76,
  • the negative electrode sheet 70 is overlaid with a slight shift in the width direction.
  • the electrode active material layer non-formed portions of the positive electrode sheet 40 and the negative electrode sheet 70 are respectively wound core portions (that is, the positive electrode active material layer forming portion of the positive electrode sheet 40). And a portion where the negative electrode active material layer forming portion of the negative electrode sheet 70 and the two separator sheets 76 are wound tightly).
  • a positive electrode lead terminal 79 and a negative electrode lead terminal 78 are respectively attached to the protruding portion (that is, the non-formed portion of the positive electrode mixture layer) 40A and the protruding portion of the negative electrode side (that is, the non-formed portion of the negative electrode active material layer) 70A. Are electrically connected to the positive terminal 74 and the negative terminal 72, respectively.
  • the constituent elements other than the positive electrode sheet 40 constituting the wound electrode body 80 may be the same as the electrode body of the conventional lithium secondary battery, and are not particularly limited.
  • the negative electrode sheet 70 may be formed by applying a negative electrode active material layer mainly composed of a negative electrode active material for a lithium secondary battery on a long negative electrode current collector.
  • a copper foil or other metal foil suitable for the negative electrode is preferably used.
  • the negative electrode active material one or more of materials conventionally used in lithium secondary batteries can be used without any particular limitation.
  • Preferable examples include carbon materials such as graphite carbon and amorphous carbon, lithium transition metal composite oxides (lithium titanium composite oxides, etc.), lithium transition metal composite nitrides, and the like.
  • separator sheet 76 used between the positive and negative electrode sheets 40 and 70
  • a sheet made of a porous polyolefin-based resin can be cited.
  • a separator may not be necessary (that is, in this case, the electrolyte itself can function as a separator).
  • the wound electrode body 80 is accommodated in the main body 84 from the upper end opening of the case main body 84 and an electrolytic solution containing an appropriate electrolyte is disposed (injected) in the case main body 84.
  • the electrolyte is lithium salt such as LiPF 6, for example.
  • a nonaqueous electrolytic solution obtained by dissolving a suitable amount (for example, concentration 1M) of a lithium salt such as LiPF 6 in a mixed solvent of diethyl carbonate and ethylene carbonate (for example, a mass ratio of 1: 1) can be used.
  • the opening is sealed by welding or the like with the lid 86, and the assembly of the lithium secondary battery 100 according to the present embodiment is completed.
  • the sealing process of the case 82 and the process of placing (injecting) the electrolyte may be the same as those used in the production of a conventional lithium secondary battery, and do not characterize the present invention. In this way, the construction of the lithium secondary battery 100 according to this embodiment is completed.
  • the lithium secondary battery 100 thus constructed is excellent because it is constructed using at least one of the electrodes manufactured by applying the method using the microbubble-containing binder solution 50 described above. It shows battery performance. For example, by constructing a battery using the electrode, it is possible to provide a lithium secondary battery 100 that satisfies at least one of excellent output characteristics, high cycle durability, and good productivity.
  • the production of the battery electrode capable of reducing the interface resistance between the current collector and the active material layer A method can be provided.
  • the battery according to the present invention (for example, a lithium secondary battery) has excellent battery performance as described above, it can be suitably used as a power source for a motor (electric motor) mounted on a vehicle such as an automobile.
  • a motor electric motor mounted on a vehicle such as an automobile.
  • the present invention provides a vehicle (typically an automobile, particularly a hybrid automobile, an electric automobile, a fuel cell automobile) provided with such a battery (which may be in the form of an assembled battery) 100 as a power source.
  • An automobile equipped with an electric motor such as 1) is provided.

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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
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PCT/JP2009/070649 2009-12-10 2009-12-10 電池用電極の製造方法 WO2011070661A1 (ja)

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CN200980162820.8A CN102656723B (zh) 2009-12-10 2009-12-10 电池用电极的制造方法
JP2011545020A JP5397711B2 (ja) 2009-12-10 2009-12-10 電池用電極の製造方法
PCT/JP2009/070649 WO2011070661A1 (ja) 2009-12-10 2009-12-10 電池用電極の製造方法
KR1020127017772A KR101389596B1 (ko) 2009-12-10 2009-12-10 전지용 전극의 제조 방법
US13/513,865 US8877386B2 (en) 2009-12-10 2009-12-10 Battery electrode production method

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US9806336B2 (en) 2012-09-21 2017-10-31 Toyota Jidosha Kabushiki Kaisha Positive electrode for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery
JPWO2018097316A1 (ja) * 2016-11-28 2019-06-24 株式会社村田製作所 負極、電池、電池パック、電子機器、電動車両、蓄電装置および電力システム
JPWO2018110133A1 (ja) * 2016-12-16 2019-10-24 株式会社日立製作所 二次電池用電極、二次電池、それらの製造方法

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WO2015045929A1 (ja) * 2013-09-25 2015-04-02 トヨタ自動車株式会社 全固体電池
KR102302761B1 (ko) * 2014-01-29 2021-09-14 제온 코포레이션 전기 화학 소자용 전극 및 전기 화학 소자
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JP6834870B2 (ja) * 2017-09-15 2021-02-24 トヨタ自動車株式会社 非水電解質二次電池およびその製造方法
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CN111900357B (zh) * 2020-08-13 2021-12-03 珠海冠宇电池股份有限公司 一种负极片及包括该负极片的锂离子电池
WO2022164280A1 (ko) * 2021-01-29 2022-08-04 주식회사 엘지화학 전극
JP7301082B2 (ja) * 2021-03-08 2023-06-30 プライムプラネットエナジー＆ソリューションズ株式会社 二次電池用電極の製造方法および二次電池の製造方法
WO2023146378A1 (ko) * 2022-01-28 2023-08-03 주식회사 엘지에너지솔루션 전극 및 이를 포함하는 전기화학소자

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KR20120094105A (ko) 2012-08-23
JPWO2011070661A1 (ja) 2013-04-22
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KR101389596B1 (ko) 2014-04-29
CN102656723A (zh) 2012-09-05
CN102656723B (zh) 2014-09-24
US8877386B2 (en) 2014-11-04

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