WO2014049788A1 - 電極用ペーストの製造方法および二次電池 - Google Patents
電極用ペーストの製造方法および二次電池 Download PDFInfo
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- WO2014049788A1 WO2014049788A1 PCT/JP2012/074946 JP2012074946W WO2014049788A1 WO 2014049788 A1 WO2014049788 A1 WO 2014049788A1 JP 2012074946 W JP2012074946 W JP 2012074946W WO 2014049788 A1 WO2014049788 A1 WO 2014049788A1
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- Prior art keywords
- electrode paste
- defoaming tank
- paste
- defoaming
- vacuum
- Prior art date
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/0036—Flash degasification
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
- B29B7/06—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices
- B29B7/10—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary
- B29B7/18—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with more than one shaft
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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
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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
- H01M4/0483—Processes of manufacture in general by methods including the handling of a melt
-
- 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
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
- H01M4/20—Processes of manufacture of pasted electrodes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
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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
Definitions
- the present invention relates to a method for manufacturing an electrode paste and a technique for a secondary battery manufactured using the electrode paste manufactured by the manufacturing method.
- a kneading machine that is, a kneading machine including a hollow barrel and two rotating shafts provided in parallel in the kneading chamber formed inside the barrel at a predetermined interval from each other.
- a twin-screw extrusion kneader in the kneading chamber, having a binder feeding portion to which the binder is supplied downstream of the powder feeding portion to which the powder is fed in the conveying direction of the powder.
- the powder processing unit is provided between the powder input unit and the binder input unit.
- the powder processing unit includes a spacer that is provided on the rotating shaft and compresses the powder.
- Japanese Patent Application No. 2012-151920 (not disclosed at the time of filing this application) a technology related to an electrode paste manufacturing system that combines a twin-screw extrusion kneader and a Mono pump.
- the electrode paste manufacturing system disclosed in Japanese Patent Application No. 2012-151920 it is not necessary to batch-process the electrode paste generated by the twin-screw extrusion kneader, and in the piping path for transferring to the defoaming tank Therefore, it is possible to continuously perform vacuum defoaming to shorten the time required for manufacturing the electrode paste.
- the electrode paste manufactured by the electrode paste manufacturing system disclosed in Japanese Patent Application No. 2012-151920 is then defoamed in a defoaming tank.
- it takes time for the defoaming treatment and even if the electrode paste manufacturing system disclosed in Japanese Patent Application No. 2012-151920 is used, There was a problem that the manufacturing time could not be shortened as expected.
- the bubbles in the electrode paste cannot be sufficiently removed, and the electrode paste excluding the part containing bubbles is used. There was also a problem that the yield of paste could not be improved as expected.
- the present invention has been made in view of such current problems, and has been produced by a method for producing an electrode paste capable of easily and reliably removing bubbles from the produced electrode paste, and the production method. It aims at providing the secondary battery manufactured using the paste for electrodes.
- the first invention is for an electrode comprising a step of evacuating the inside of the defoaming tank while introducing the electrode paste into the defoaming tank to vacuum degas the bubbles contained in the electrode paste.
- a method for producing a paste wherein in the step of vacuum degassing bubbles contained in the electrode paste, the electrode in the defoaming tank is adjusted by adjusting a flow rate of the electrode paste introduced into the defoaming tank. The rising speed of the liquid level of the paste for use is made smaller than the rising speed of the bubbles in the electrode paste.
- the step of vacuum defoaming bubbles contained in the electrode paste is performed by using an electrode paste manufacturing system including a twin screw extrusion kneader and a Mono pump, and discharging the twin screw extrusion kneader.
- the outlet and the suction port of the mono pump are connected, and the discharge port of the mono pump is connected to the defoaming tank, and the suction port of the vacuum pump is connected to the defoaming tank, and the rotor-stator contact portion in the mono pump
- the degassing tank side piping system from the hermetic line is configured as a closed circuit with the hermetic line formed at the boundary as a boundary, and the vacuum pump is used to evacuate the defoaming tank and the degassing tank is degassed from the hermetic line. While the piping system on the foam tank side is maintained in a vacuum state, the electrode paste is transferred to the defoaming tank by the Morno pump, and the airtight line is transferred. Within the more the defoaming tank piping system inside and the defoaming tank, by continuously vacuum degassing treatment the electrode paste is being implemented.
- connection port farther from the shaft seal portion of the motor shaft of the MONO pump is the suction port
- connection port closer to the shaft seal portion of the motor shaft is the suction port
- a fourth invention is manufactured using the electrode paste manufactured by the method for manufacturing an electrode paste according to any one of claims 1 to 3.
- the first invention and the second invention can reliably remove bubbles contained in the electrode paste.
- bubbles contained in the electrode paste can be more reliably removed by the electrode paste manufacturing system with a simple configuration.
- a quality electrode body with less defects such as see-through can be produced, and this improves the performance of the secondary battery. Can contribute.
- the figure which shows the removal condition of the bubble contained in the electrode paste in the manufacturing method of the electrode paste which concerns on one Embodiment of this invention (a) The cross-sectional schematic diagram which shows the introduction condition of the electrode paste to a defoaming tank, (B) The schematic diagram for demonstrating the relationship between the liquid level rise speed of the paste for electrodes, and the bubble rise speed of the bubble contained in this electrode paste.
- an electrode paste manufacturing system 1 is a system for manufacturing an electrode paste 8, and includes a twin-screw extrusion kneader 2, a buffer tank 3, and a Mono pump 4.
- the defoaming tank 6 and the vacuum pump 7 are provided.
- the manufacturing method of the paste for electrodes which concerns on this invention is realizable by manufacturing the paste 8 for electrodes using the paste manufacturing system 1 for electrodes.
- the biaxial extrusion kneader 2 is an apparatus used for kneading a plurality of types of powders and liquids, and includes a hollow barrel (not shown) and a kneading chamber (not shown) formed inside the barrel. , Two rotation shafts (not shown) provided in parallel with a predetermined interval are provided.
- the twin-screw extrusion kneader 2 is supplied with powder (active material or thickener) or liquid (solvent) in the kneading chamber, transports the powder and liquid while compressing, and is added during the kneading.
- the liquid (solvent) and powder (binder) are fed into the kneading chamber and further conveyed while being compressed, so that each powder and liquid are kneaded to produce the electrode paste 8. (See FIG. 3).
- the buffer tank 3 is a tank for temporarily storing the electrode paste 8 generated by the twin-screw extrusion kneader 2 before it is introduced into the MONO pump 4, and is discharged from the twin-screw extrusion kneader 2. It plays a role of absorbing fluctuations in the discharge amount of the electrode paste 8. For this reason, the buffer tank 3 is omitted when the discharge amount of the electrode paste 8 from the twin-screw extrusion kneader 2 is controlled so that the supply amount of the electrode paste 8 by the MONO pump 4 matches. Is also possible.
- the MONO pump 4 is a pump classified as a rotary positive displacement single screw eccentric screw pump, and is used as a means for transferring the electrode paste 8 generated by the twin screw extrusion kneader 2 toward the defoaming tank 6. Yes.
- the Mono pump 4 is a pump having a structure including a rotor 4b and a stator 4c inside a casing 4a.
- the rotor 4b is a metal rod that is curved in a substantially spiral shape with a predetermined twist angle, and is configured such that the cross-sectional shape thereof is a perfect circle at any location.
- the stator 4c is a member made of an elastic material (for example, EPDM) in which a gap for inserting the rotor 4b is formed.
- the Mono pump 4 is configured to form an air tight line that ensures air tightness between the primary side and the secondary side of the Mono pump 4 at a portion where the rotor 4b and the stator 4c are in contact with each other.
- the casing 4a of the MONO pump 4 includes a suction port 4e for introducing the electrode paste 8 toward the inside of the casing 4a, and a discharge port 4f for discharging the electrode paste 8 from the casing 4a.
- the MONO pump 4 has a suction port 4 e side connected to the buffer tank 3, and a discharge port 4 f side connected to a defoaming tank 6 by a pipe 5.
- filters 5a and 5a for removing foreign substances contained in the electrode paste 8 are provided.
- the rotor 4b is connected to a rotating shaft 4h fixed to the shaft of a motor (not shown) via a universal joint 4g.
- the rotor 4b can be rotated in the stator 4c.
- the electrode paste 8 introduced into the casing 4a from the suction port 4e is sucked into the cavity 4d on the most upstream side (with the open end) in the transfer direction.
- the cavities 4d, 4d,... Move to the discharge port 4f side of the Mono pump 4. That is, in the MONO pump 4, the electrode paste 8 sucked into the cavities 4d, 4d,... Is continuously transferred in the direction of the discharge port 4f, and finally discharged from the discharge port 4f.
- the Mono pump 4 can also use the suction port 4e side as a discharge port and the discharge port 4f side as a suction port by reversing the rotation direction of a motor (not shown).
- a plurality of independent cavities 4d, 4d,... are formed as gaps between the rotor 4b and the stator 4c, and the contact between the rotor 4b and the stator 4c is between the cavities 4d, 4d,. Airtightness is secured at the position (tangential position).
- the piping system on the primary side of the airtight line with the airtight line (that is, the contact position between the rotor 4 b and the stator 4 c) in the Mono pump 4 is used as the boundary.
- the piping system on the secondary side of the hermetic line can be a sealed circuit while being an open circuit communicating with the buffer tank 3.
- the defoaming tank 6 is a container for storing the electrode paste 8, and the defoaming tank 6 is depressurized (for example, about ⁇ 90 kPa) and mixed in the electrode paste 8. It is equipment for removing the bubbles by rising and breaking the bubbles by expanding the bubbles.
- the vacuum pump 7 is connected to the defoaming tank 6 and is a facility for evacuating the defoaming tank 6.
- the vacuum level in the defoaming tank 6 can reach about -90 kPa. Has the ability to do.
- the degree of vacuum (pressure P1 shown in FIG. 1) on the secondary side of the filters 5a and 5a is ⁇ 90 kPa.
- the degree of vacuum (pressure P2 shown in FIG. 1) on the primary side of the filters 5a and 5a can be set to about ⁇ 35 kPa.
- the electrode paste 8 generated by the twin-screw extrusion kneader 2 is received by the buffer tank 3, and the defoaming tank is received from the buffer tank 3 by the mono pump 4. Transfer to 6.
- the electrode paste 8 generated in the defoaming tank 6 is transferred by the MONO pump 4, the entire amount of the electrode paste 8 is once stored in the defoaming tank 6 (that is, after batch processing).
- the inside of the defoaming tank 6 is evacuated by the vacuum pump 7, and the electrode paste 8 is subjected to vacuum defoaming to remove bubbles.
- the piping system on the secondary side of the airtight line in the MONO pump 4 is a sealed circuit.
- the paste 8 can be continuously subjected to vacuum defoaming processing without batch processing on the path (pipe 5) from the mono pump 4 to the defoaming tank 6.
- the inlet 6c is formed above the trunk
- the term “above” here is a concept including a part above the body part 6a and an upper part in the body part 6a, and the electrode paste 8 introduced into the defoaming tank 6 from the introduction port 6c. Any position that can flow down along the inner wall surface 6b is acceptable.
- the electrode paste 8 introduced into the defoaming tank 6 from the introduction port 6c flows down the inner wall surface 6b of the body 6a and is stored in the bottom 6d of the defoaming tank 6.
- the electrode paste 8 stored in the bottom 6d of the defoaming tank 6 has a predetermined speed according to the flow rate of the electrode paste 8 supplied from the inlet 6c (hereinafter referred to as supply flow rate Q). Then the liquid level rises.
- the rising speed of the liquid level of the electrode paste 8 is referred to as a liquid level rising speed V L
- the liquid level rising speed V L is a horizontal break in the internal space of the body portion 6 a of the defoaming tank 6.
- the electrode paste 8 supplied per unit time forms a thin film having a predetermined thickness according to the supply flow rate Q on the liquid surface.
- a paste having a high specific gravity such as battery paste 8
- the density difference becomes large under reduced pressure, and the paste immediately after supply and the paste from which bubbles have already been removed are separated into two layers. Therefore, a thin film is stably formed.
- the bubbles contained in the electrode paste 8 constituting the thin film rise toward the liquid surface at a predetermined speed. In the following, it referred to a rising speed of gas bubbles in the electrode paste 8 as bubble rising velocity V G.
- the bubble rising velocity V G is based on the equation of Stokes, it can be calculated by Equation 2 below.
- r shown in Formula 2 is the radius of the bubble
- ⁇ L in Formula 2 is the density of the electrode paste 8
- ⁇ G is the density of the bubble
- ⁇ is the viscosity of the electrode paste 8. It is.
- the manufacturing method of the electrode paste according to the present embodiment defines a reference radius r a minimum value of the radius r of the bubble to be removed from the electrode paste 8. That is, in the electrode paste 8 shown in this embodiment, the reference radius r a size greater than the bubble should be removed, may include the size of the bubbles is less than the reference radius r a is allowed . Then, in the manufacturing method of the electrode paste according to an embodiment of the present invention, the liquid level rising speed V L, the size is the reference radius r a bubble of the bubble rise velocity V G (hereinafter, the reference bubble rising velocity V smaller than the called a Ga) (i.e., the liquid level rising speed V L ⁇ reference bubble rising velocity V Ga) has a configuration.
- the rotational speed of the motor of the Mono pump 4 is set to reduce the liquid level rising speed V L compared to the reference bubble rising speed V Ga. Is controlled by an inverter to adjust the supply flow rate Q of the electrode paste 8 to the defoaming tank 6.
- the bubbles contained in the electrode paste 8 are put on the stored electrode paste 8 as shown in FIG. Before a thin film is formed by the next electrode paste 8, it can float up to the gas-liquid interface. Bubbles that rise to the gas-liquid interface and appear on the liquid surface are expanded to a size that cannot be maintained by the surface tension of the surfactant at the gas-liquid interface, and are easily and reliably broken. Therefore, bubbles of the reference radius r a size greater than that contained in the electrode paste 8 is reliably removed from the said electrode paste 8.
- the electrode paste 8 introduced into the defoaming tank 6 flows down while forming a thin film on the inner wall surface 6b of the body 6a, so that the thin film on the inner wall surface 6b in a reduced pressure state is also broken. Even before the bubbles are promoted and stored in the bottom 6d of the defoaming tank 6, the bubbles are removed from the electrode paste 8.
- the defoaming tank 6 shown in FIG. 6A exemplifies the case where the cross-sectional area in the horizontal section of the body portion 6a is constant, but the electrode paste according to the present embodiment
- the shape of the defoaming tank 6 used in the manufacturing method is not limited to this.
- the defoaming tank 6 has an arm-shaped bottom shown in FIGS. 1, 3 and 4 and has a shape in which the cross-sectional area of the body 6a is not constant. The structure which has may be sufficient.
- the electrode in the electrode paste manufacturing system 1 according to this embodiment is illustrated.
- the structure of the supply means of the paste 8 for use is not limited to this.
- As a means for supplying the electrode paste 8 in the electrode paste manufacturing system 1 according to this embodiment for example, the degree of vacuum in the defoaming tank 6 is increased and the electrode paste 8 stored in the buffer tank 3 is sucked. It is good also as a structure introduced into the defoaming tank 6.
- the electrode paste manufacturing method includes the electrode paste 8 introduced into the defoaming tank 6 while evacuating the inside of the defoaming tank 6 and included in the electrode paste 8.
- the flow rate of the electrode paste 8 to be introduced into the defoaming tank 6 (supply flow rate Q) is By adjusting, the rising speed (liquid level rising speed V L ) of the electrode paste 8 in the defoaming tank 6 is compared with the rising speed of bubbles in the electrode paste 8 (reference bubble rising speed V Ga ). It is to make it smaller.
- the process of carrying out the vacuum degassing of the bubble contained in the electrode paste 8 is a paste manufacturing system for electrodes provided with the twin-screw extrusion kneader 2 and the Mono pump 4. 1 is used to connect the discharge port of the twin-screw extrusion kneader 2 and the suction port 4e of the MONO pump 4 and connect the discharge port 4f of the MONO pump 4 to the defoaming tank 6 and also connect the suction port of the vacuum pump 7 to the suction port 4e.
- the defoaming tank 6 side piping system (pipe 5) is configured as a sealed circuit with the airtight line formed at the contact portion between the rotor 4b and the stator 4c in the MONO pump 4 connected to the defoaming tank 6 as a boundary.
- the vacuum pump 7 evacuates the defoaming tank 6 and maintains the piping system (pipe 5) on the defoaming tank 6 side from the airtight line in a vacuum state, while the mono pump Then, the electrode paste 8 is transferred to the defoaming tank 6, and the electrode paste 8 is continuously fed into the defoaming tank 6 side piping system (pipe 5) and the defoaming tank 6 from the airtight line. It is implemented by vacuum defoaming treatment. With such a configuration, bubbles contained in the electrode paste 8 can be reliably removed.
- the configuration of the electrode paste manufacturing system according to the second embodiment of the present invention will be described with reference to FIGS.
- the MONO pump 4 is different from the electrode paste manufacturing system 1 according to the first embodiment of the present invention.
- the connection direction is reversed.
- connection port of the MONO pump 4 used as the suction port 4e in the electrode paste manufacturing system 1 is arranged downstream in the transfer direction of the electrode paste 8 (that is, used as a discharge port) and discharged.
- the other connection port that has been used as the outlet 4f is configured to be arranged on the upstream side in the transfer direction of the electrode paste 8 (that is, used as a suction port).
- the MONO pump 4 is arranged in this manner, and the motor (not shown) is rotated in the reverse direction, so that the MONO pump 4 transfers the electrode paste 8 and the MONO pump 4 motor (not shown) side.
- the inside of the casing 4a can be evacuated, and air can be introduced into the casing 4a from the shaft seal portion of the rotating shaft 4h.
- the electrode paste 8 supplied into the defoaming tank 6 can be energized and scattered by the air flowing in the pipe 5,
- the scattered electrode paste 8 can collide with the liquid surface of the electrode paste 8 stored in the bottom 6d of the defoaming tank 6 so that bubbles floating on the liquid surface can be broken more reliably.
- the MONO pump 4 uses the connection port (discharge port 4f) farther from the shaft seal portion of the motor shaft included in the MONO pump 4 as a suction port.
- the connection port (suction port 4e) closer to the shaft seal part of the shaft is used as the suction port.
- electrode pastes manufactured using the electrode paste manufacturing systems 1 and 11 will be described.
- the bubbles contained in the electrode paste 8 are more reliably removed than in the prior art.
- Defects (through-through) that occur when the paste 8 is applied to a metal foil are reduced.
- by manufacturing a secondary battery from the electrode paste 8 manufactured using the electrode paste manufacturing system 1 or 11 internal defects of the secondary battery can be reduced, and the reliability of the secondary battery is improved. It can contribute to quality improvement.
- the air bubbles are removed from the whole in the state of being stored in the defoaming tank 6, and it is necessary to remove the supernatant. Since all the electrode pastes 8 generated can be used, the yield of the electrode paste 8 is improved as compared with the conventional case. For this reason, it can contribute to the cost reduction of a secondary battery by manufacturing a secondary battery from the electrode paste 8 manufactured using the electrode paste manufacturing system 1 * 11.
- the secondary battery according to one embodiment of the present invention is manufactured using the electrode paste 8 manufactured by the electrode paste manufacturing method according to one embodiment of the present invention.
- the electrode paste 8 from which bubbles are reliably removed it is possible to manufacture a high quality electrode body with less defects such as see-through, and thereby improve the performance of the secondary battery. Can contribute.
- the present invention can be widely applied not only as an electrode paste for manufacturing a secondary battery, but also as a method for manufacturing a paste that needs to remove bubbles in the paste. It can be applied as a technique for producing chemical products, chemicals, and the like.
- Electrode paste manufacturing system 2 Twin screw extrusion kneader 4 Mono pump 6 Defoaming tank 7 Vacuum pump 8 Electrode paste
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Abstract
Description
このような二軸押出混練機を用いて、電極合剤(電極用ペースト)を生成することによって、良質な(即ち、均質な)ペーストの生成を可能にしている。
このため、二軸押出混練機を用いて電極用ペーストを生成する場合、バッチ処理を行う分だけ生成時間が長くなるため、二軸押出混練機を用いた場合には、電極用ペーストの生成に要する時間の短縮を図ることが困難であった。
斯かる特願2012-151920において開示された電極用ペースト製造システムを用いることにより、二軸押出混練機で生成された電極用ペーストをバッチ処理する必要がなくなり、脱泡タンクへ移送する配管経路中において、連続的に真空脱泡を行うことを可能にして、電極用ペーストの製造に要する時間の短縮を図っている。
しかしながら、電極用ペーストに対する脱泡処理方法の如何によっては、脱泡処理に時間を要してしまい、特願2012-151920において開示された電極用ペースト製造システムを使用しても、電極用ペーストの製造に要する時間を思うように短縮できないという問題があった。
また、脱泡処理方法の如何によっては、電極用ペースト中の気泡を十分に除去することができず、気泡が含まれている部分を除いた電極用ペーストを使用することになるため、電極用ペーストの歩留まりを、思うように改善できないという問題もあった。
まず始めに、本発明の第一の実施形態に係る電極用ペーストの製造システムの全体構成について、図1から図5を用いて説明をする。
図1に示す如く、本発明の第一の実施形態に係る電極用ペースト製造システム1は、電極用ペースト8を製造するためのシステムであり、二軸押出混練機2、バッファタンク3、モーノポンプ4、脱泡タンク6、真空ポンプ7等を備える構成としている。
そして、電極用ペースト製造システム1を使用して電極用ペースト8を製造することにより、本発明に係る電極用ペーストの製造方法を実現することができる。
そして、二軸押出混練機2は、混練室に粉体(活物質や増粘材)や液体(溶媒)が供給され、粉体および液体を圧縮等しながら搬送し、また混練途中で、追加の液体(溶媒)や粉体(結着剤)を混練室に供給しつつ、さらに圧縮等しながら搬送して、各粉体および液体を混練して、電極用ペースト8を生成するものである(図3参照)。
このためバッファタンク3は、二軸押出混練機2からの電極用ペースト8の排出量とモーノポンプ4による電極用ペースト8の供給量が一致するように制御等している場合には、省略することも可能である。
ロータ4bは、所定のひねり角度を持ちながら略螺旋状に湾曲する金属製の棒状体であり、いずれの箇所においても、その断面形状が真円になるように構成されている。
また、ステータ4cは、ロータ4bを挿入するための空隙部が形成されている弾性を有する材料(例えば、EPDM)からなる部材である。
また換言すると、モーノポンプ4では、ロータ4bとステータ4cが接触する部位で、該モーノポンプ4の一次側と二次側の気密性を確保する気密ラインを形成する構成としている。
そして図1に示す如く、モーノポンプ4は、吸込口4e側がバッファタンク3に接続されており、また、吐出口4f側が、配管5によって脱泡タンク6に接続されている。
また、該配管5上には、電極用ペースト8に含まれる異物を除去するためのフィルタ5a・5aを設けている。
即ち、モーノポンプ4では、各キャビティ4d・4d・・・内に吸い込まれた電極用ペースト8が、吐出口4fの方向へと連続的に移送され、最終的に、吐出口4fから排出される。
尚、モーノポンプ4は、モータ(図示せず)の回転方向を反転させることにより、吸込口4e側を吐出口とし、吐出口4f側を吸込口として使用することも可能である。
また、電極用ペースト製造システム1では、脱泡タンク6からモーノポンプ4に至る配管経路を密閉回路としているため、フィルタ5a・5aの二次側における真空度(図1に示す圧力P1)を-90kPa程度とすることができ、また、フィルタ5a・5aの一次側における真空度(図1に示す圧力P2)を-35kPa程度とすることができる。
このように、モーノポンプ4で脱泡タンク6に生成された電極用ペースト8を移送するとき、脱泡タンク6で電極用ペースト8の全量を一旦貯溜してから(即ち、バッチ処理してから)、真空ポンプ7により脱泡タンク6の内部を真空引きして、電極用ペースト8を真空脱泡処理して、気泡を除去する構成としている。
そして導入口6cは、脱泡タンク6における略円柱状の部位である胴部6aの上方に形成しており、導入口6cから脱泡タンク6内に導入された電極用ペースト8が、鉛直な内壁面となっている胴部6aの内壁面6bに沿って下方に向けて流れて、底部6dにおいて貯溜されるように構成している。
尚、ここでいう「上方」とは、胴部6aよりも上の部位と、胴部6aにおける上部を含む概念であり、導入口6cから脱泡タンク6内に導入された電極用ペースト8を、内壁面6bに沿って流下させることができる位置であればよい。
図6(a)に示す如く、導入口6cから脱泡タンク6に導入された電極用ペースト8は、胴部6aの内壁面6bを流下していき、脱泡タンク6の底部6dに貯溜されていく。
このとき、脱泡タンク6の底部6dに貯溜される電極用ペースト8は、導入口6cから供給される電極用ペースト8の流量(以下、供給流量Qと記載する)に応じて、所定の速度で液面が上昇していく。
尚以下では、電極用ペースト8の液面の上昇速度のことを液面上昇速度VLと呼び、液面上昇速度VLは、脱泡タンク6の胴部6aの内部空間の水平方向における断面積をAとするとき、以下に示す数式1により求めることができる。
電池用ペースト8のように比重が大きいペースト中に気泡が混入している場合、減圧環境下では密度差が大きくなって、供給直後のペーストと既に気泡が除去されているペーストが二層に分離するため、安定的に薄膜が形成される。
そして、その薄膜を構成する電極用ペースト8に含まれる気泡は、所定の速度で、液面に向けて上昇していく。
尚以下では、電極用ペースト8における気泡の上昇速度のことを気泡上昇速度VGと呼ぶ。
そして、気泡上昇速度VGは、ストークスの式に基づき、以下に示す数式2によって算出することができる。
尚、数式2中に示すrは気泡の半径であり、また、数式2中のρLは電極用ペースト8の密度であり、ρGは気泡の密度であり、ηは電極用ペースト8の粘度である。
即ち、本実施形態で示す電極用ペースト8においては、基準半径ra以上の大きさの気泡は除去すべきであり、基準半径ra未満の大きさの気泡が含まれることは許容している。
そして、本発明の一実施形態に係る電極用ペーストの製造方法では、液面上昇速度VLを、大きさが基準半径raである気泡の気泡上昇速度VG(以下、基準気泡上昇速度VGaと呼ぶ)に比して小さくする(即ち、液面上昇速度VL<基準気泡上昇速度VGa)構成としている。
気液界面まで浮上し液面に出現した気泡は、該気液界面において、界面活性剤による表面張力では気泡を維持することができない大きさにまで膨張して、容易かつ確実に破泡されるため、電極用ペースト8に含まれていた基準半径ra以上の大きさの気泡が、該電極用ペースト8中から確実に除去される。
このような断面積が一定でない脱泡タンク6を用いる場合、液面高さと断面積との関係を予め知得しておくとともに、該脱泡タンク6に導入される電極用ペースト8の液面高さを図示しない液面センサ等で検出し、液面高さに従って、電極用ペースト8の供給流量Qを制御する構成とすることも可能である。
そして、液面高さに応じて電極用ペースト8に供給流量Qを制御することにより、液面上昇速度VLを基準気泡上昇速度VGaに比して大きい値に維持する構成としてもよい。
本実施形態に係る電極用ペースト製造システム1における電極用ペースト8の供給手段としては、例えば、脱泡タンク6内の真空度を高めて、バッファタンク3に貯溜される電極用ペースト8を吸引して脱泡タンク6内に導入する構成としてもよい。
またこの場合、脱泡タンク6内に電極用ペースト8を導入する配管の途中に流量調整弁を設けて、該流量調整弁の開度や脱泡タンク6内の真空度を調整することによって、脱泡タンク6内に導入する電極用ペースト8の供給流量Qを調整する構成としてもよい。
このような構成により、電極用ペースト8に含まれる気泡を確実に除去することができる。
図7および図8に示す如く、本発明の第二の実施形態に係る電極用ペースト製造システム11では、本発明の第一の実施形態に係る電極用ペースト製造システム1に対して、モーノポンプ4の接続方向を逆向きにする構成としている。
このような構成により、簡易な構成の電極用ペースト製造システム11によって、電極用ペースト8に含まれる気泡をより確実に除去することができる。
これまでに説明をした各電極用ペースト製造システム1・11を用いて製造した電極用ペースト8では、電極用ペースト8に含まれる気泡が従来に比して確実に除去されているため、その電極用ペースト8を金属箔に塗工したときに生じる不良(透け)が低減されている。
このため、電極用ペースト製造システム1・11を用いて製造した電極用ペースト8から二次電池を製造することによって、二次電池の内部不良を低減することができ、二次電池の信頼性向上等の品質改善に寄与することができる。
このため、電極用ペースト製造システム1・11を用いて製造した電極用ペースト8から二次電池を製造することによって、二次電池のコスト低減に寄与することができる。
このように、気泡が確実に除去された電極用ペースト8を使用することにより、透け等の不良が少ない品質のよい電極体を製造することができ、またこれにより、二次電池の性能向上に寄与することができる。
2 二軸押出混練機
4 モーノポンプ
6 脱泡タンク
7 真空ポンプ
8 電極用ペースト
Claims (4)
- 脱泡タンクに電極用ペーストを導入しつつ、前記脱泡タンクの内部を真空引きして、前記電極用ペーストに含まれる気泡を真空脱泡する工程を備える電極用ペーストの製造方法であって、
前記電極用ペーストに含まれる気泡を真空脱泡する前記工程において、
前記脱泡タンクに導入する前記電極用ペーストの流量を調整して、
前記脱泡タンクにおける前記電極用ペーストの液面の上昇速度を、
前記電極用ペーストにおける気泡の上昇速度に比して小さくする、
ことを特徴とする電極用ペーストの製造方法。 - 前記電極用ペーストに含まれる気泡を真空脱泡する前記工程は、
二軸押出混練機とモーノポンプを備える電極用ペーストの製造システムを用いて、
前記二軸押出混練機の排出口と前記モーノポンプの吸込口を接続し、かつ、
前記モーノポンプの吐出口を脱泡タンクに接続するとともに、真空ポンプの吸込口を前記脱泡タンクに接続し、
前記モーノポンプにおけるロータとステータの接触部において形成する気密ラインを境界として、該気密ラインより前記脱泡タンク側の配管系を密閉回路に構成し、
前記真空ポンプにより、前記脱泡タンクから真空排気をして、前記気密ラインより前記脱泡タンク側の配管系を真空状態に維持しつつ、
前記モーノポンプにより前記脱泡タンクに前記電極用ペーストを移送して、
前記気密ラインより前記脱泡タンク側の配管系の内部および前記脱泡タンクの内部において、前記電極用ペーストを連続的に真空脱泡処理することにより、実施される、
ことを特徴とする請求項1に記載の電極用ペーストの製造方法。 - 前記モーノポンプは、
該モーノポンプが有するモータ軸の軸封部により遠い側の接続口を前記吸込口とし、
前記モータ軸の軸封部により近い側の接続口を前記吸込口とする、
ことを特徴とする請求項2に記載の電極用ペーストの製造方法。 - 前記請求項1から請求項3のいずれか一項に記載された電極用ペーストの製造方法により製造された前記電極用ペーストを用いて製造された、
ことを特徴とする二次電池。
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