WO2013191125A1 - フィルム外装電池 - Google Patents
フィルム外装電池 Download PDFInfo
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- WO2013191125A1 WO2013191125A1 PCT/JP2013/066569 JP2013066569W WO2013191125A1 WO 2013191125 A1 WO2013191125 A1 WO 2013191125A1 JP 2013066569 W JP2013066569 W JP 2013066569W WO 2013191125 A1 WO2013191125 A1 WO 2013191125A1
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- WIPO (PCT)
- Prior art keywords
- film
- interface
- clad battery
- layer
- power generation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
- H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/102—Primary casings, jackets or wrappings of a single cell or a single battery characterised by their shape or physical structure
- H01M50/105—Pouches or flexible bags
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
- H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure
- H01M50/126—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure comprising three or more layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/14—Primary casings, jackets or wrappings of a single cell or a single battery for protecting against damage caused by external factors
- H01M50/145—Primary casings, jackets or wrappings of a single cell or a single battery for protecting against damage caused by external factors for protecting against corrosion
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/183—Sealing members
- H01M50/186—Sealing members characterised by the disposition of the sealing members
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/131—Primary casings, jackets or wrappings of a single cell or a single battery characterised by physical properties, e.g. gas-permeability or size
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
- Y10T29/49112—Electric battery cell making including laminating of indefinite length material
Definitions
- the present invention relates to a battery in which a power generation element is housed in a film-shaped packaging material and a method for manufacturing the same, and more particularly to a film-clad battery with high long-term reliability and a method for manufacturing the same.
- Lithium ion batteries having large capacity density and mass density are mounted not only for portable devices such as mobile phones and digital cameras, but also for electric bicycles, electric motorcycles, electric cars, and the like. With the diversification of battery applications, there are increasing demands for battery weight reduction and design freedom.
- a battery exterior body a film-like exterior material obtained by laminating a metal container, an aluminum foil, or the like and a synthetic resin film is used.
- a power generation element including a positive electrode and a negative electrode is covered with a film-shaped packaging material, and the positive electrode terminal and the negative electrode terminal are hermetically sealed so as to lead out to the outside of the film-shaped packaging material.
- the outer package of the battery has a role of preventing leakage of the electrolyte inside and moisture intrusion into the battery, and this sealing portion has been devised in various ways to influence the reliability of the battery.
- a resin lump 32 is provided at the inner end portion of the storage portion 6 a of the electrode element 6 of the cohesive weld portion 19 that is a weld portion of a metal laminate resin film case.
- Patent Document 1 has the following problems when gas is generated inside the battery due to repeated charging / discharging or use in a high temperature environment. That is, as shown in FIG. 11, the power generation element 6 swells, the film-shaped exterior material 4 is deformed, and stress concentrates on the boundary between the resin mass 32 and the heat welding layer 13. As a result, a crack is generated by the resin fracture peeling portion 17 from the heat welding layer 13 toward the barrier layer 12. When the cracked portion of the barrier layer 12 and the electrolytic solution come into contact with each other, corrosion of aluminum or the like of the barrier layer 12 occurs, and there is a risk that the film-like exterior material may have defects such as holes or cracks that lead to the outside, resulting in leakage of the electrolytic solution. It was.
- An object of the present invention is to accommodate a power generation element in which a positive electrode and a negative electrode are opposed via a separator in a film-shaped exterior material in which at least a welding layer, a barrier layer, and a protective layer are laminated, and the film-shaped exterior including the power generation element
- a battery-clad battery having a sealing portion that seals the periphery of the material, and is adjacent to the aggregated weld portion formed on at least a part of the sealed portion, and the power generation element storage portion side of the aggregated welded portion This can be solved by a film-clad battery having a first interfacial adhesive portion arranged.
- an interfacial adhesive portion is provided adjacent to the power generation element side of the cohesive weld portion formed in at least a part of the sealing portion of the film-shaped exterior material. Therefore, when the film-clad battery is expanded by the gas generated inside the battery, the sealing part is cleaved along the interface adhesion part. As a result, the agglomerated welded portion is not damaged, and a barrier layer such as a metallic barrier layer that is an inner layer of the film-shaped exterior material can be prevented from being corroded by the electrolytic solution. Therefore, a film-clad battery excellent in long-term reliability can be provided.
- FIG. 1 is a plan view illustrating an example of a film-clad battery according to the present invention.
- FIG. 2 is a diagram for explaining an embodiment of the present invention, and is a cross-sectional view showing a part of the A-A ′ cross section of FIG. 1.
- FIG. 3 is a diagram for sequentially explaining the sealing step of the film-clad battery of the present invention, and is a cross-sectional view of the AA ′ cross section in FIG. 1, FIG. 3A explains the heating step, and FIG.
- FIG. 3C is a diagram illustrating a sealing part after completion.
- FIG. 4 is a diagram for explaining another embodiment of the present invention, and is a cross-sectional view taken along the line A-A ′ in FIG. 1.
- FIG. 4 is a diagram for explaining another embodiment of the present invention, and is a cross-sectional view taken along the line A-A ′ in FIG. 1.
- FIG. 4 is a diagram for explaining another embodiment of the present invention, and is a cross
- FIG. 5 is a diagram for explaining another embodiment of the present invention, and is a cross-sectional view taken along the line A-A ′ in FIG. 1.
- FIG. 6 is a view for explaining another embodiment of the present invention, and is a cross-sectional view taken along the line A-A ′ in FIG. 1.
- FIG. 7 is a diagram for explaining another embodiment of the present invention, and is a cross-sectional view taken along the line A-A ′ in FIG. 1.
- FIG. 8 is a diagram for explaining an embodiment of the present invention, and is a cross-sectional view taken along the line A-A ′ in FIG. 1.
- FIG. 9 is a view for explaining an embodiment of the present invention, and is a cross-sectional view taken along the line A-A ′ in FIG. 1.
- FIG. 10 is a view for explaining a conventional film-clad battery, and is a cross-sectional view of a portion corresponding to the A-A ′ cross section in FIG. 1.
- FIG. 11 is a diagram for explaining a conventional film-clad battery, and is a cross-sectional view of a portion corresponding to the A-A ′ cross section in FIG. 1.
- FIG. 1 is a plan view illustrating an example of a film-clad battery according to the present invention.
- the film-clad battery 1 has a positive electrode terminal 2 and a negative electrode terminal 3 joined to each of a positive electrode extraction terminal and a negative electrode extraction terminal attached to a power generation element.
- the positive electrode terminal 2 and the negative electrode terminal 3 are protruded from the film-shaped exterior material 4, and a heat-welded portion 5 is formed around the film-shaped exterior material 4 and sealed.
- FIG. 1 shows an example in which the power generation element is housed by two members provided with a power generation element housing portion and then the entire periphery of both members is sealed, but this is due to another sealing method. Also good.
- a film-shaped exterior material is folded to house a power generation element.
- the thing etc. which sealed after storing an electric power generation element in the accommodating part formed by press molding can be mentioned.
- what sealed after making a power generation element accommodate in the member which processed the film-form exterior material into the cylinder shape or the envelope shape can also be used.
- the power generation element a laminated body in which a plurality of positive electrodes, separators, and negative electrodes are laminated in order, or a wound body in which a belt-like laminated body is wound can be used.
- FIG. 2 is a partially cutaway view showing a cross section taken along the line AA ′ of the film-clad battery shown in FIG. 1 of the present invention.
- the film-shaped packaging material 4 that houses the battery element 6 includes a surface protective layer 11 that protects the outer surface, a barrier layer 12 such as a metal barrier layer that blocks permeation of gas, and the penetration of the electrolyte solution.
- the heat welding layer 13 is formed by heat welding.
- the surface protective layer 11 can be made of a synthetic resin material that has ductility that does not break during processing of the film-shaped exterior material 4 and has a higher melting point or softening point than the heat-welded layer. Of these, resins having sufficient ductility during processing and having a high melting point or softening point are preferred, and specific examples include nylon or polyethylene terephthalate.
- the barrier layer 12 various types such as a metal or metal oxide vapor-deposited layer and a metal film can be used as long as the barrier layer 12 has a ductility that prevents gas permeation and does not break during processing.
- an aluminum or aluminum alloy foil having high ductility and excellent workability is desirable.
- the heat welding layer 13 include a synthetic resin layer that has corrosion resistance to the electrolytic solution and has excellent adhesive strength at the time of heat welding. Specifically, those containing one or more of polyolefin synthetic resins such as polypropylene and polyethylene, and modified polyolefin resins can be used.
- the surface protective layer 11, the barrier layer 12, and the heat-welded layer 13 are not limited to those composed of only one layer, but may be a laminate of two or more layers. In the case where a plurality of layers are laminated, a plurality of layers having different characteristics may be laminated.
- the cohesive weld layer is formed by the heat weld layer reaching the melting point and melting and integrating.
- an agglomerated welded portion 19 that is in contact with the side opposite to the storage portion 6a side of the interface adhesive portion 15 and is formed with the heat-welded layer in a molten state.
- a range in which the interface adhesion portion 15 exists is referred to as an interface adhesion region 15a
- a range in which the aggregation weld portion 19 exists is referred to as an aggregation adhesion region 19a.
- the film-clad battery 1 of the present invention has an interfacial adhesion portion 15 in contact with the aggregation weld portion 19.
- the interface bonding portion 15 where the boundary surface remains between the heat-welded layers only cleaves along the boundary surface. Therefore, the aggregated bonding portion 19 is not damaged, and the barrier layer can be prevented from being exposed.
- FIG. 3 is a diagram for explaining a method for producing a film-clad battery according to the present invention. It is a figure which shows the cross section in AA 'of the film-clad battery shown in FIG. 1 of this invention, and is a figure which notched one part. As shown to FIG. 3A, it presses with the two heating members 21 from both surfaces of the sealing part 18, and it heats until the welding surface of a heat welding layer will be in a molten state. Next, after removing the heating member 21, as shown in FIG. 3B, the region located at the boundary with the embossed portion is cooled by two cooling members 22 from both sides. The cooling region is a region where the heating member is pressed and a region on the storage unit 6a side of the adjacent battery element 6. As a result, the cohesive welded portion 19 is prevented from growing in crystal grains due to recrystallization, and the interface bonding portion 15 is formed in the sealing portion 18 near the portion where the heating member is pressed.
- each side of the outer periphery of the film-shaped exterior material is sealed by heat welding except for the side where the electrolytic solution is injected, and the periphery of each side is predetermined.
- the shape was cut.
- the electrolyte solution injection part was thermally welded in the same manner as the other parts to obtain a film-clad battery.
- FIG. 4 is a diagram for explaining another embodiment of the present invention.
- FIG. 2 is a view of the film-clad battery shown in FIG.
- the sealing portion 18 of the film-shaped exterior material 4 includes a cohesive welded portion 19 and an interface adhesive portion 15, and the interface adhesive portion includes a curved portion 31.
- the battery of this embodiment is formed by causing a slight shift in the sandwiching of the film-shaped exterior material by two heated heating members (not shown). That is, the sealing part formed by generating a shift in the region of the sealing part 18 where the thermal welding layer is softened is shown.
- the end surface on the embossed portion side of one heating member is formed by extruding the heat-welded layer of the film-shaped exterior material 4 to the embossed portion side more than the other. That is, when the battery element 6 is pushed out toward the storage portion 6a, a curved portion 31 whose interface is curved is generated in the interface adhesive portion 15.
- the interfacial adhesive portion 15 can be similarly formed in the battery element storage portion 6a of the cohesive weld portion 19 even when a slight displacement of the mutual heating members occurs.
- the interfacial bonded portion 15 whose length is increased by bending exhibits a greater resistance to cleavage.
- FIG. 5 is a diagram for explaining another embodiment of the present invention.
- FIG. 2 is a view in which a part of the AA ′ section of the film-clad battery shown in FIG. 1 of the present invention is cut away.
- the sealing portion 18 of the film-shaped exterior material 4 is provided with a cohesive weld portion 19 and an interface adhesive portion 15, and a resin lump 32 is provided at the interface adhesive portion.
- the end surfaces of two heating members are flattened at the boundary between the embossed part and the flat part of the storage part 6a of the battery element 6 as compared with that shown in FIG. It is close to the border.
- FIG. 6 is a diagram for explaining another embodiment of the present invention.
- FIG. 2 is a view in which a part of the AA ′ section of the film-clad battery shown in FIG. 1 of the present invention is cut away.
- the following points are different from the method shown in FIG. That is, the end surfaces of the two heating members (not shown) are brought closer to the flat boundary side between the embossed portion and the flat portion of the storage portion 6a of the battery element 6. Furthermore, some positional deviation is caused in the two heating members.
- FIG. 6 illustrates a sealing portion in a case where a shift is caused in a region where the heat-welded layer is melted.
- the resin mass 32 extruded during heat welding is illustrated as separated from the heat welding layer on the inner surface of the film-shaped exterior material.
- the boundary of the heat-welded layer is not clearly separated, and the extruded resin mass and the heat-welded layer on the inner surface of the film-shaped exterior material are integrally formed.
- FIG. 7 is a diagram for explaining another embodiment of the present invention.
- FIG. 2 is a view in which a part of the AA ′ section of the film-clad battery shown in FIG. 1 of the present invention is cut away.
- the battery of the embodiment of FIG. 7 shows a battery in which the resin mass 32 is generated in a different part from that shown in FIG. That is, as compared with the one shown in FIG. 6, the deviation amount of the sandwich of the film-like exterior material by the two heating members is made larger. Moreover, the end surface of the heating part is sealed close to the flat part boundary between the embossed part and the film-like exterior material. As a result, the amount of resin pushed out to the inside of the battery is increased.
- the curved portion 31 is formed in the interface bonding portion 15 as a result of the resin being pushed out in an uneven manner corresponding to the amount of displacement of the heating member.
- the curved portion 31 formed in the interface bonding portion 15 has a longer interface length of the interface bonding portion and has a higher strength against cleavage, as shown in FIG. As a result, it has a great effect in preventing a decrease in strength against damage of the cohesive welded portion 19.
- FIG. 8 is a diagram for explaining another embodiment of the present invention.
- FIG. 2 is a view showing a cross-section of the film-clad battery shown in FIG. 1 of the present invention, taken along the line AA ′.
- the embodiment of FIG. 8 is a diagram for explaining a state in which the interfacial adhesive peeling portion 16 is formed at the end portion of the interfacial adhesive portion 15 as a result of an increase in the pressure inside the film-shaped exterior material.
- the portion close to the inside of the power generation element side 6a of the interface adhesive portion 15 having a low strength is selectively cleaved because the end portion has a strength lower than that of the cohesive weld portion 19. Conceivable.
- the interfacial adhesive peeling portion 16 is generated. Even if the interfacial adhesive peeling portion 16 occurs, the entire interfacial adhesive portion 15 is not cleaved, the aggregate welded portion 19 is damaged, and the barrier layer 12 such as aluminum is not exposed.
- FIG. 9 is a diagram for explaining another embodiment of the present invention.
- FIG. 2 is a view in which a part of the AA ′ section of the film-clad battery shown in FIG. 1 of the present invention is cut away.
- the embodiment of FIG. 9 is a diagram for explaining a state in which the interfacial adhesive peeling portion 16 is generated in the resin mass 32 provided at the end portion of the interfacial adhesive portion 15 as a result of an increase in the pressure inside the film-shaped exterior material. .
- the end portion of the interface bonding portion 15 is selectively cleaved at the end portion of the interface bonding portion 15 that is close to the inside of the power generation element.
- the interfacial adhesive peeling portion 16 is generated. Even if the interfacial adhesive peeling portion 16 occurs, the entire interfacial adhesive portion 15 is not peeled off, the cohesive weld portion 19 is not damaged, or the barrier layer 12 such as aluminum is not exposed.
- the resin lump 32 is formed in contact with the interface bonding portion 15, and as a result, the cracking stops inside the resin lump 32, thereby providing a battery that does not affect the interface bonding portion 15. can do.
- Example 1 (Preparation of positive electrode) A positive electrode slurry was prepared by kneading 92 parts by mass of lithium manganate (LiMn2O4) powder, 5 parts by mass of carbon black, and 3 parts by mass of polyvinylidene fluoride together with NMP. The obtained positive electrode slurry was coated on both sides of an aluminum foil having a thickness of 20 ⁇ m and dried, and then the positive electrode surface was pressed with a roll.
- LiMn2O4 lithium manganate
- the aluminum foil coated with the positive electrode active material was cut to produce a positive electrode in which a positive electrode tab having a length of 15 mm and a width of 10 mm was integrally formed on a positive electrode having a length of 105 mm and a width of 55 mm.
- a negative electrode slurry was prepared by kneading 91 parts by mass of graphite, 1 part by mass of carbon black, and 8 parts by mass of polyvinylidene fluoride together with NMP.
- the obtained negative electrode slurry was applied and dried on both sides of a copper foil having a thickness of 10 ⁇ m, and then the negative electrode surface was pressed with a roll.
- the copper foil coated with the negative electrode active material was cut to prepare a negative electrode in which a negative electrode tab having a length of 12 mm and a width of 10 mm was integrally formed on a negative electrode having a length of 109 mm and a width of 59 mm.
- the produced positive electrode and negative electrode were alternately laminated with a polypropylene separator having a length of 111 mm, a width of 59 mm, and a thickness of 25 ⁇ m so that the outermost layer became a negative electrode, thereby producing a power generation element.
- the number of stacked layers was 15 positive electrodes and 16 negative electrodes.
- An aluminum foil having a length of 30 mm, a width of 10 mm, and a thickness of 200 ⁇ m was used as a positive electrode lead terminal for leading out to the outside of the film-shaped outer package. Moreover, it joined to the positive electrode tab of the positive electrode which laminated
- a copper foil having a length of 30 mm, a width of 10 mm, and a thickness of 200 ⁇ m was used as the negative electrode lead terminal for the negative electrode. Moreover, it joined to the negative electrode tab which laminated
- the following laminated films were used as the film exterior material.
- Surface protective layer 25 ⁇ m thick nylon barrier layer: 40 ⁇ m thick aluminum foil
- Adhesive inner layer 50 ⁇ m thick polypropylene film having a random-block-random three-layer structure with a melting point of 145 ° C. and a softening point of 120 ° C.
- Two film-shaped exterior materials having a length of 180 mm and a width of 100 mm and a thickness of 115 ⁇ m were prepared.
- a recess having a length of 120 mm, a width of 70 mm, and a depth of 3 mm was formed by embossing in the center of the film-shaped exterior material.
- the power generation element was housed in a recess formed by embossing, and the positive electrode lead terminal and the negative electrode lead terminal were led out from the film exterior material from one side.
- a side where the lead terminal is taken out and two sides which are in contact with the side where the lead terminal is taken out are sealed to form a positive electrode terminal and a negative electrode terminal.
- the side opposite to the side from which both electrode terminals were taken out was used as the injection side, and the electrolyte solution was injected and finally the injection side was sealed.
- the electrolytic solution an electrolytic solution containing LiPF6 as a lithium salt in a mixed solvent composed of ethylene carbonate and diethyl carbonate was used.
- the terminal side is two heating members with a temperature of 180 ° C. and a width of 5 mm, and the end face on the embossed part side of the heating member is 0.5 mm away from the embossed part of the film-like exterior material to the flat part side from the flat part boundary. Placed in position. Subsequently, it was sandwiched and sealed for 6 seconds so that the distance between the two heating members was 0.2 mm. Thereafter, two cooling members with a width of 5.6 mm at 25 ° C. were arranged at positions where the end faces of the two cooling members on the embossed portion side became the boundary between the embossed portion and the flat portion. Subsequently, it cooled by pinching
- the electrolyte solution was injected from the injection side into the film-clad battery before injection prepared as described above. After that, two heating members with a width of 7.5 mm whose heating side was heated to 170 ° C., the end surface on the embossed part side of the heating member is 0.5 mm from the boundary between the flat part of the embossed part and the film-like exterior material Arranged at a distance. Subsequently, it was sealed by being sandwiched and heated for 5 seconds so that the distance between the heating members was 0.075 mm.
- the aggregated welding layer and the interfacial adhesive layer are formed at all the welding locations by setting the temperature according to the welding location.
- Example 2 One of the two heating members in Example 1 was arranged such that the end surface of the heating member was 0.5 mm from the boundary between the embossed portion and the flat portion of the film exterior material. Further, the other heating member was sealed by placing the end face of the heating member at 0.6 mm from the flat part boundary between the embossed part and the film exterior material to the flat part side. Other conditions were the same as in Example 1 to produce a film-clad battery. As a result, a film-clad battery having a cross-sectional structure in FIG. 4 was obtained.
- Example 3 The heating member in Example 1 was sealed by setting the end surface of the heating member to 0.3 mm from the flat part boundary between the embossed part and the film-shaped exterior material to the flat part side. Other conditions were the same as in Example 1 to produce a film-clad battery. As a result, a film-clad battery having a cross-sectional structure shown in FIG. 5 was obtained. In this case, the end surface of the heating member is sealed close to the boundary side between the embossed portion and the flat portion of the film-shaped exterior material by a distance of 0.3 mm from the boundary between the embossed portion and the film-shaped exterior material. As a result, a heat-welded layer pushed inward from the sealing portion is generated and formed as a resin lump 32. The manufactured battery was subjected to a deterioration acceleration test in the same manner as in Example 1, and the results are shown in Tables 1 and 2.
- Example 4 One of the heating members in Example 3 was 0.3 mm from the boundary between the embossed portion and the flat portion of the film-shaped exterior material on the end surface of the heating member. Further, the other heating member was sealed so that the end surface on the embossed part side of the heating member became 0.4 mm from the flat part boundary between the embossed part and the film-shaped exterior material to the flat part side. Other conditions were the same as in Example 1 to produce a film-clad battery. As a result, a film-clad battery having a cross-sectional structure shown in FIG. 6 was obtained. The manufactured battery was subjected to a deterioration acceleration test in the same manner as in Example 1, and the results are shown in Tables 1 and 2.
- Example 5 One heating member in Example 4 was moved 0.2 mm from the flat part boundary between the embossed part and the film-shaped exterior material to the flat part side of the heating member. Further, the other heating member was sealed by placing the end surface on the embossed part side of the heating member at a distance of 0.4 mm from the flat part boundary between the embossed part and the film-shaped exterior material to the flat part side. Other conditions were the same as in Example 3 to produce a film-clad battery. As a result, a film-clad battery having a cross-sectional structure shown in FIG. 7 was obtained.
- Example 6 Table 1 and Table 2 show the results of accelerated deterioration tests performed in the same manner as in Example 1, except that the cooling by each cooling member in Example 1 was performed 4 seconds after the completion of heating by the heating member.
- Example 7 A deterioration acceleration test was conducted in the same manner as in Example 1 except that the cooling by each cooling member in Example 1 was 4 seconds after the completion of heating heat by the heating member in Example 1, and the results are shown in Tables 1 and 2 below. It is shown in 2.
- Example 8 Table 1 and Table 2 show the results of accelerated deterioration tests performed in the same manner as in Example 1, except that the cooling by each cooling member in Example 3 was performed 4 seconds after the completion of heating by the heating member.
- Example 9 Table 1 and Table 2 show the results of acceleration tests conducted in the same manner as in Example 1 except that the cooling by each cooling member in Example 4 was performed 4 seconds after the completion of heating by the heating member.
- Example 10 A deterioration acceleration test was performed in the same manner as in Example 1 except that the cooling by each cooling member in Example 5 was 4 seconds after the completion of heating by the heating member, and the results are shown in Tables 1 and 2.
- Comparative Example 1 By setting the temperature of the heating member at the time of thermal welding of the sealing portion to 200 ° C. for the terminal extraction side, 180 ° C. for the side side, and 190 ° C. for the liquid injection side, the temperature of the thermal welding portion of each sealing portion is set. 155 to 165 ° C. As a result, the welding temperature of the heat-welded portion was set to a temperature sufficiently higher than the melting point, so that the sealing portion and the resin block consisted of only the crystal portion. Other conditions were the same as in Example 3 to produce a film-clad battery. As a result, as shown in FIG. 10, a resin lump 32 was formed in the aggregation weld portion 19. A deterioration acceleration test was performed in the same manner as in Example 1, and the results are shown in Tables 1 and 2.
- Comparative Example 2 A battery was fabricated in the same manner as in Comparative Example 1 except that the cooling by each cooling member in Comparative Example 1 was 4 seconds after the completion of overheating. A deterioration acceleration test was performed in the same manner as in Example 1, and the results are shown in Tables 1 and 2.
- Evaluation test method 1 Tensile test results The produced batteries were tested by the following evaluation methods, and the results are shown in the table.
- the film exterior material on the side surface portion was cut to a width of 15 mm and a length of 50 mm in the direction perpendicular to the heat welding direction to prepare a test piece for a tensile test.
- This test piece was bent so that two unwelded portions were in a straight line, and a T-shaped test piece was produced.
- One of the unwelded portions of the T-shaped test piece was fixed, and the other was pulled with a tensile gauge in the vertical direction at a speed of 10 mm / min, and the position where the maximum tensile strength and exposure of the aluminum layer were observed was confirmed.
- the results are shown in Table 1.
- the tensile strength was about 140 N / 15 mm in Examples 1 to 5 and Comparative Example 1 in which the time until cooling after heating was 1 second. Further, in Examples 6 to 10 and Comparative Example 2 where the time until cooling after heating was 4 seconds, it was around 110 N / 15 mm. It is considered that this is because the recrystallization of the heat-welded layer has progressed due to the increase in the interval until cooling, and the embrittlement of the agglomerated weld portion has progressed.
- the distance to the exposure of the aluminum layer was 0.5 mm in Examples 1 and 3, 0.6 mm in Example 2, 0.7 mm in Example 4, and 0. It became 9 mm.
- Example 1 Tensile strength (N / 15mm) Aluminum layer exposed position (mm) Example 1 143 0.5 Example 2 141 0.6 Example 3 138 0.5 Example 4 142 0.8 Example 5 144 0.9 Example 6 112 0.5 Example 7 115 0.6 Example 8 114 0.5 Example 9 112 0.8 Example 10 116 0.9 Comparative Example 1 140 0.0 Comparative Example 2 142 0.0
- Evaluation test method 2 Results of accelerated deterioration test The following tests were carried out after 40 of each of Examples 1 to 10 and Comparative Examples 1 and 2 were fully charged. By fixing the thickness direction of the battery at a fixed size with an aluminum jig, only the vicinity of the welded portion was expanded. The battery deterioration acceleration test was performed by leaving 20 pieces in a 70 ° C. environment for 2 months and the remaining 20 pieces in a 85 ° C. environment for 2 months. About these test batteries, the presence or absence of the swelling of 10% or more of volume ratios before a test and the presence or absence of electrolyte leakage were confirmed by attaching a litmus test paper in the vicinity of the sealing portion of the outer package. For the case where the outer body was confirmed to be swollen, the AA ′ cross-sectional state in FIG. 1 was observed.
- the adhesive portion 15 has a lower strength than the heat-welded layer or the cohesive welded portion 19 that is integrally bonded to the cooling portion after heating, so that the end portion of the interface adhesive portion 15 is preferentially peeled off. It is believed that there is. In addition, for the case where the resin lump was formed in contact with the interface bonding portion, peeling stopped on the surface in the resin lump, and it was confirmed that even the sealing portion did not reach. Furthermore, as in Examples 2, 4, 5, 7, 9, and 10, in which the distorted part is formed in the interface adhesive part, the separation distance is the same, but the distance of the interface adhesive layer is extended by the curve, respectively, The adhesive strength of the interface adhesive portion is larger than those of Examples 1, 3, 6, and 8.
- Comparative Examples 1 and 2 in which swelling was observed, 3 and 5 were cracked at the boundary of the heat-welded layer on the side opposite to the resin block and the sealing portion as shown in FIG. The layer was exposed to the inner side, and corrosion by the electrolyte was confirmed.
- the interface adhesion part is provided adjacent to the power generation element side of the cohesive weld part formed on at least a part of the sealing part of the film-like exterior material laminated with a protective layer, a barrier layer such as a metal foil, and a heat welding layer
- a barrier layer such as a metal foil
- a heat welding layer As a result of preventing the agglomerates and agglomerates formed at the ends of the agglomerated welds from becoming the starting point of cleavage, the film-like exterior is also expanded even when the film-like exterior battery is expanded by the gas generated inside the battery. It is possible to provide a film-clad battery having excellent long-term reliability by preventing the barrier layer such as the metal foil of the material from being exposed and corroding by the electrolytic solution.
- SYMBOLS 1 Film-clad battery, 2 ... Positive electrode terminal, 3 ... Negative electrode terminal, 4 ... Film-shaped exterior material, 6 ... Battery element, 6a ... Storage part of a battery element, DESCRIPTION OF SYMBOLS 11 ... Surface protective layer, 12 ... Barrier layer, 13 ... Thermal welding layer, 15 ... Interfacial adhesion part, 16 ... Interfacial welding peeling part, 17 ... Resin breaking peeling part, 18 ... Sealing part, 19 ... Cohesive weld part, 21 ... Heating member, 22 ... Cooling member, 32 ... Resin lump
Abstract
Description
電池の外装体としては、金属容器やアルミニウム箔等と合成樹脂フィルムを積層したフィルム状外装材などを利用している。なかでも上記要求を満たす電池として、軽量かつ形状の自由度が高いフィルム状外装材を用いたフィルム外装電池の需要が高まっている。
例えば、特許文献1は、図10で示すように、金属ラミネート樹脂フィルムケースの溶着部である凝集溶着部19の電極要素6の収納部6aの内側端部に樹脂塊32を設けている。これによって接合界面を曲面とし、応力を樹脂塊32の両端に分散されるようにすることで電池の気密性を高めることを提案している。
また、特許文献2には、フィルム状外装材の熱溶着部内側に溶着加工をしていない部分を設けている。これによって、樹脂のはみ出しによる切り欠き部状の部位の発生を防止して剥離強度の低下を防止することを提案している。
すなわち、図11で示す様に、発電要素6が膨らみ、フィルム状外装材4が変形し、樹脂塊32と熱溶着層13の境界に応力が集中する。その結果、熱溶着層13からバリア層12に向けて樹脂破断剥離部17による亀裂が生じる。
亀裂部分のバリア層12と電解液が接触することによりバリア層12のアルミニウム等の腐食が生じ、フィルム状外装材に穴、亀裂等の外部に通じる欠損が生じ、電解液が漏出するおそれがあった。
図1は、本発明のフィルム外装電池の一例を説明する図であり、平面図である。
フィルム外装電池1は、発電要素に装着した正極引出端子と負極引出端子のそれぞれに接合した正極電極端子2と負極電極端子3とを有している。
正極電極端子2および負極電極端子3をフィルム状外装材4から突出させ、フィルム状外装材4の周囲に熱溶着部5を形成して封口したものである。
例えば、一枚のフィルム状外装材を折り曲げて発電要素を収納したもの。あるいは、プレス成形によって形成した収納部に発電要素を収納した後に密閉したもの等を挙げることができる。
また、フィルム状外装材を筒状、あるいは封筒状に加工した部材に発電要素を収納した後に封口したものも用いることができる。
また、図1で説明した例のように同一の辺から正極電極端子2と負極電極端子3を取り出すものに限らない。それぞれの端子を対向する辺等のように別の辺から取り出したものであっても良い。
また、発電要素には、正極電極、セパレーター、負極電極を順に複数枚を積層した積層体、あるいは、帯状の積層体を巻回した巻回体等も用いることができる。
電池要素6を収納したフィルム状外装材4は、外面を保護する表面保護層11、気体の透過を阻止する金属バリア層等のバリア層12、電解液の浸透を防止し、フィルム状外装材を熱溶着する熱溶着層13で構成している。
表面保護層11には、フィルム状外装材4の加工時に破断しない程度の延性を有し、熱溶着層よりも融点または軟化点が高い合成樹脂材料を用いることができる。なかでも、加工時の延性が充分に得られ、高い融点,又は軟化点を持つ樹脂が好ましく、具体的にはナイロンまたはポリエチレンテレフタレートを挙げることができる。
熱溶着層13は、電解液に対して耐食性があって、熱溶着時の接着強度が優れた合成樹脂層を挙げことができる。具体的には、ポリプロピレン、ポリエチレン等のポリオレフィン系の合成樹脂、変成ポリオレフィン樹脂の一種または複数種を含むものを用いることができる。
フィルム状外装材4の封止部18の電池要素6の収納部6a側には、凝集溶着層は熱溶着層が融点に達して溶融し、一体化することで生成する。熱溶着層が軟化・半溶解した状態で加圧することで数μm程度の熱溶着層の食い込みが起こり生成する界面接着部15が存在している。
また、界面接着部15の収納部6a側とは反対側に接して、熱溶着層が溶融状態となって形成された凝集溶着部19が存在している。
なお、以下の説明においては、界面接着部15が存在している範囲を界面接着領域15aと称し、凝集溶着部19が存在している範囲を凝集接着領域19aと称している。
図3Aに示すように、封止部18の両面から2本の加熱部材21によって押圧して熱溶着層の溶着面が溶融状態となるまで加熱する。
次いで、加熱部材21を取り除いた後に、図3Bに示すように両面から2本の冷却部材22によってエンボス加工部との境界部に位置する領域の冷却を行う。冷却領域は、加熱部材を押し当てた領域と、隣接する電池要素6の収納部6a側の領域である。これによって、凝集溶着部19が再結晶化で結晶粒が大きくなることを防止するとともに、加熱部材を押し当てた部分の近傍の封止部18に界面接着部15を形成する。
フィルム状外装材4の封止部18は凝集溶着部19と界面接着部15を備えており、界面接着部は湾曲部31を備えている。
この実施形態の電池は、加熱した2本の加熱部材(図示せず)によるフィルム状外装材の挟み込みに多少のずれを発生させて形成したものである。すなわち、封止部18の熱溶着層を軟化する領域にずれを発生させて形成した封止部を示している。
すなわち、電池要素6の収納部6a側へと押し出したことで界面接着部15に、その界面が湾曲した湾曲部31が生じたものである。
本発明では、相互の加熱部材の多少の位置ずれか生じた場合であっても、凝集溶着部19の電池要素の収納部6aには界面接着部15を同様に形成することができる。また湾曲によって長さが長くなった界面接着部15は開裂に対してより大きな抵抗力を発揮する。
フィルム状外装材4の封止部18に凝集溶着部19と界面接着部15を備えており、界面接着部に樹脂塊32を備えている。
この実施形態の電池は、図3で示したものに比べて2本の加熱部材(図示せず)の端面を、電池要素6の収納部6aのエンボス加工部と平坦部との境目の平坦部境目側へ近づけたものである。その結果、封止部よりも内側へ押し出した熱溶着層が発生し、それが樹脂塊32を形成したものと考えられる。
生じた樹脂塊32は界面接着部15と一体に生成しているので、界面接着部15は凝集溶着部19までの距離が長くなる。その結果、樹脂塊32の端部から始まる開裂が凝集溶着部19に達するまでの余裕度が大きくなるという作用を果たす。
この実施形態では、図3で示した方法に比べて以下の点が相違している。
すなわち、2本の加熱部材(図示せず)の端面を、電池要素6の収納部6aのエンボス加工部と平坦部との境目の平坦部境目側へ近づけている。更に、2本の加熱部材に多少の位置ずれを生じさせている。図6では、熱溶着層が溶融する領域にずれを生じさせた場合の封止部を説明している。
その結果、封止部よりも内側へ押し出した熱溶着層が発生し、それが樹脂塊32として形成されると共に、界面の湾曲部31を形成したものと考えられる。また、湾曲部31によって界面接着部15の長さが長くなり、開裂に対する強度が大きくなるとともに、樹脂塊32によって封止部18の強度が高められるものと考えられる。
図7の実施形態の電池は、図6で示したものとは2本の加熱部材の位置ずれの相違のために樹脂塊32が異なる部分に生成したものを示している。
すなわち、図6に示したものに比べて2本の加熱部材によるフィルム状外装材の挟み込みのずれ量をより大きくしている。また、加熱部の端面をエンボス加工部とフィルム状外装材の平坦部境目に近づけて封止している。その結果、電池内部側へ押し出す樹脂量を多くしたものである。したがって、加熱部材のずれ量に相当して樹脂が偏って押し出された結果、界面接着部15に湾曲部31を形成したものと考えられる。
界面接着部15に形成した湾曲部31は、図6で示したものと同様に界面接着部の界面の長さが長くなって開裂に対する強度が大きくなっている。その結果、凝集溶着部19の損傷に対する強度の低下を防止する上では大きな効果を奏するものである。
図8の実施の形態は、フィルム状外装材の内部の圧力が上昇した結果、界面接着部15の端部に界面接着剥離部16を形成した状態を説明する図である。
このように、内部圧力の上昇時には、まず強度が小さい界面接着部15の発電要素側6aの内部に近い部分が端部が凝集溶着部19より強度が小さいために、選択的に開裂するものと考えられる。
その結果、界面接着剥離部16を生じるものと考えられる。界面接着剥離部16が生じても界面接着部15の全体の開裂、あるいは凝集溶着部19の損傷、アルミニウム等のバリア層12が露出することはない。
図9の実施の形態は、フィルム状外装材の内部の圧力が上昇した結果、界面接着部15の端部に設けた樹脂塊32に界面接着剥離部16が生成した状態を説明する図である。
内部圧力の上昇時には、まず界面接着部15の発電要素側の内部に近い部分の端部に、界面接着部15の端部が選択的に開裂する。その結果、界面接着剥離部16が生成するものと考えられる。界面接着剥離部16が生じても界面接着部15の全体の剥離や凝集溶着部19の損傷、あるいはアルミニウム等のバリア層12が露出することはない。
加えて、この例で示す様に界面接着部15に接して樹脂塊32を形成しているので、樹脂塊32の内部で開裂が止まる結果、界面接着部15には影響を及ぼさない電池を提供することができる。
実施例1
(正極の作製)
マンガン酸リチウム(LiMn2O4)粉末92質量部、カーボンブラック5質量部、ポリフッ化ビニリデン3質量部をNMPと共に混練して正極スラリーを調製した。得られた正極スラリーを厚さ20μmのアルミニウム箔の両面に塗布乾燥の後、ロールによって正極面を押圧した。
次いで、正極活物質を塗布したアルミニウム箔を切断し、長さ105mm、幅55mmの正極に、長さ15mm、幅10mmの正極タブを一体に形成した正極電極を作製した。
グラファイト91質量部、カーボンブラック1質量部、ポリフッ化ビニリデン8質量部をNMPと共に混練して負極スラリーを調製した。得られた負極スラリーを厚さ10μmの銅箔の両面に塗布乾燥の後、ロールによって負極面を押圧した。
次いで、負極活物質を塗布した銅箔を切断し、長さ109mm、幅59mmの負極に、長さ12mm、幅10mmの負極タブを一体に形成した負極電極を作製した。
作製した正極電極と負極電極を、長さ111mm、幅59mm、厚さ25μmのポリプロピレン製のセパレーターを介して最外層が負極となるように交互に積層して発電要素を作製した。それぞれの積層枚数は、正極電極15枚、負極電極16枚とした。
フィルム状外装体の外部に導出するための正極リード端子として長さ30mm、幅10mm、厚さ200μmのアルミニウム箔を用いた。また、封口時にフィルム状外装材と一体となる合成樹脂層を形成したアルミリード端子を積層した正極電極の正極タブに接合した。
また、負極電極にも負極リード端子として長さ30mm、幅10mm、厚さ200μmの銅箔を用いた。また、封口時にフィルム状外装材と一体となる合成樹脂層を形成した銅製リード端子を積層した負極タブに接合した。
フィルム外装材としては、以下の積層フィルムを用いた。
表面保護層:厚さ25μmのナイロン製
バリア層:厚さ40μmのアルミニウム箔
接着性内面層:厚さ50μmの融点145℃、軟化点120℃のランダム-ブロック-ランダム三層構造を有するポリプロピレンフィルム
上記の長さ180mm、幅100mmの厚さ115μmのフィルム状外装材を2枚用意した。このフィルム状外装材の中央に長さ120mm、幅70mm、深さ3mmの凹部をエンボス加工により形成した。
リード端子を取り出す辺と、リード端子を取り出す辺と接する2辺を封止して、正極電極端子、負極電極端子を形成した。
次いで、両電極端子を取り出した辺と対向する辺を注液辺として、電解液を注液して最後に注液辺を封止した。電解液としては、エチレンカーボネートおよびジエチルカーボネートからなる混合溶媒に、リチウム塩としてLiPF6を含む電解液を使用した。
この後、25℃の幅5.6mmの2本の冷却部材を、2本の冷却部材のエンボス加工部側の端面がエンボス加工部と平坦部境目となる位置に配置した。次いで、2本の冷却部材間の間隔が0.2mmとなるようにして1.5秒間挟み込んで冷却した。
この後、室温の幅10mmの2本の冷却部材を、2本の冷却部材のエンボス加工部側の端面がエンボス加工部とフィルム外装平坦部境目になる位置に配置した。冷却部材の間隔が0.15mmとなるように3秒間挟み込んで冷却した。
上記のようにして作製した注液前のフィルム外装電池に、注液辺より電解液を注入した。
この後、注液辺を170℃に加熱した幅7.5mmの2本の加熱部材を、加熱部材のエンボス加工部側の端面がエンボス加工部とフィルム状外装材の平坦部境目から0.5mm離れた位置に配置した。次いで、加熱部材の間隔が0.075mmとなるように5秒間挟み込んで加熱して封止した。
この後、室温の幅10mmの2本の冷却棒を、2本の冷却部材のエンボス加工部側の端面がエンボス加工部とフィルム状外装材の平坦部境目になる位置に配置した。次いで、冷却棒の間隔0.15mmで3秒間挟み込んで冷却した。
最後に側辺および注液辺の溶着部分を5mm残し、その他の部分を切断して外形を整えて、図2に示す断面構造を有するフィルム外装電池を得た。
実施例1における2本の加熱部材のうち一方の加熱部材を加熱部材の端面がエンボス加工部とフィルム外装材の平坦部境目から0.5mmに配置した。また、他方の加熱部材を加熱部材の端面がエンボス加工部とフィルム外装材の平坦部境目から平坦部側へ0.6mmに配置して封止を行った。
その他の条件は実施例1と同様にしてフィルム外装電池を作製した。その結果、図4に断面構造を持つフィルム外装電池を得た。
その結果、加熱部材のエンボス加工部側の端面がエンボス加工部とフィルム状外装材の平坦部境目により近い側に接しているフィルム状外装材の熱溶着層が押し出された。それによって他方の加熱部材が接しているフィルム状外装材の熱溶着層より電池内部側へ押し出された。このために界面接着部が現れる界面が歪曲した歪曲部が形成されるためと考えられる。
作製した電池を実施例1と同様に劣化加速試験を行いその結果を表1、表2に示す。
実施例1における加熱部材を、加熱部材の端面がエンボス加工部とフィルム状外装材の平坦部境目から平坦部側へ0.3mmとして封止を行った。その他の条件は実施例1と同じにしてフィルム外装電池を作製した。その結果、図5に示す断面構造を持つフィルム外装電池を得た。
これは加熱部材の端面をエンボス加工部とフィルム状外装材との境目から0.3mmの距離だけフィルム状外装材の平坦部との境目側へ近づけて封止したものである。
その結果、封止部よりも内側へ押し出した熱溶着層が発生し、それが樹脂塊32として形成したためである。
作製した電池を実施例1と同様に劣化加速試験を行いその結果を表1、表2に示す。
実施例3における一方の加熱部材を加熱部材の端面がエンボス加工部とフィルム状外装材の平坦部との境目から0.3mmとした。
また、他方の加熱部材を加熱部材のエンボス加工部側の端面をエンボス加工部とフィルム状外装材の平坦部境目から平坦部側へ0.4mmとなるようにして封止を行った。その他の条件は実施例1と同様にしてフィルム外装電池を作製した。その結果、図6に示す断面構造を持つフィルム外装電池を得た。
作製した電池を実施例1と同様に劣化加速試験を行いその結果を表1、表2に示す。
更に、界面接着部に現れる界面31が歪曲し、その歪曲部が樹脂塊32にまで及んでいるためと考えられる。
作製した電池を実施例1と同様に劣化加速試験を行いその結果を表1、表2に示す。
実施例4における一方の加熱部材を、加熱部材の端面がエンボス加工部とフィルム状外装材の平坦部境目から平坦部側へ0.2mm移動した。また、他方の加熱部材を加熱部材のエンボス加工部側の端面がエンボス加工部とフィルム状外装材の平坦部境目から平坦部側へ0.4mmに配置して封止を行った。
その他の条件は実施例3と同じにしてフィルム外装電池を作製した。その結果、図7に示す断面構造を持つフィルム外装電池を得た。
2本の加熱部材によるフィルム状外装材の挟み込みのズレをより大きくしたので加熱部材の端面がエンボス加工部とフィルム状外装材の平坦部境目に近づけて封止することとなる。
その結果、加熱部材のずれの分だけ、樹脂が偏って押し出されるとともに界面接着部に現れる界面が歪曲しためと考えられる。
作製した電池を実施例1と同様に劣化加速試験を行いその結果を表1、表2に示す。
実施例1における各冷却部材による冷却を、加熱部材による加熱熱完了後4秒後とした点を除き、実施例1と同様にして劣化加速試験を行いその結果を表1、表2に示す。
実施例2に実施例1における各冷却部材による冷却を、加熱部材による加熱熱完了後4秒後とした点を除き、実施例1と同様にして劣化加速試験を行いその結果を表1、表2に示す。
実施例3における各冷却部材による冷却を、加熱部材による加熱熱完了後4秒後とした点を除き、実施例1と同様にして劣化加速試験を行いその結果を表1、表2に示す。
実施例4における各冷却部材による冷却を加熱部材による加熱熱完了後4秒後とした点を除き実施例1と同様にして劣化加速試験を行いその結果を表1、表2に示す。
実施例5における各冷却部材による冷却を、加熱部材による加熱熱完了後4秒後とした点を除き、実施例1と同様にして劣化加速試験を行いその結果を表1、表2に示す。
封止部の熱溶着時の加熱部材の温度を端子取出辺は200℃、側辺は180℃、注液辺は190℃と設定することで、それぞれの封止部の熱溶着部の温度を155~165℃にした。
これによって、熱溶着部の溶着温度を融点より十分高い温度としたことで、封止部および樹脂塊が結晶部のみからなるようにした。
その他の条件は実施例3と同じにしてフィルム外装電池を作製した。その結果、図10に示すように凝集溶着部19には、樹脂塊32が形成された。
実施例1と同様にして劣化加速試験を行いその結果を表1、表2に示す。
比較例1における各冷却部材による冷却を過熱完了後4秒後とした点を除き比較例1と同様にして電池を作製した。
実施例1と同様にして劣化加速試験を行いその結果を表1、表2に示す。
引張り試験結果
作製した電池を以下の評価方法によって試験を行ってその結果を表に示す。
側面部のフィルム外装材を熱溶着方向に対して垂直方向に幅15mm、長さ50mmに切り取り、引っ張り試験用の試験片を作製した。この試験片を未溶着部2枚が一直線になるよう折り曲げ、T字型の試験片を作製した。このT字型試験片の未溶着部の一方を固定し、もう一方を引っ張りゲージで10mm/minの速度で鉛直方向に引っ張り、最大の引っ張り強度とアルミニウム層の露出が見られる位置を確認した。その結果を表1に示す。
アルミニウム層の露出までの距離については、比較例1、2に対し、実施例1、3では0.5mm、実施例2は0.6mm、実施例4では0.7mm、実施例5では0.9mmとなった。
また、比較例1,2に対し、実施例1~10は形成された界面接着層が裂けて凝縮溶着層に達してからアルミニウム層の露出が起きていた。また、実施例2,4,5,7,9,10においては界面接着層が湾曲することで裂ける距離が延びるため、実施例1、3、6、8よりも金属層露出までの距離が大きいためと考えられる。
引っ張り強度(N/15mm) アルミニウム層露出位置(mm)
実施例1 143 0.5
実施例2 141 0.6
実施例3 138 0.5
実施例4 142 0.8
実施例5 144 0.9
実施例6 112 0.5
実施例7 115 0.6
実施例8 114 0.5
実施例9 112 0.8
実施例10 116 0.9
比較例1 140 0.0
比較例2 142 0.0
劣化加速試験結果
以上の実施例1~10および比較例1,2についてそれぞれ40個ずつを満充電状態に充電した後に以下の試験を行った。
アルミニウム製の治具で電池の厚さ方向を定寸で固定することで溶着部分付近のみが膨れるようにした。
20個を70℃の環境下に2ヶ月間、残り20個を85℃の環境下に2ヶ月間に放置することで電池の劣化加速試験を行った。
これらの試験電池について、試験前に対して体積比10%以上の膨れの有無、外装体の封止部付近にリトマス試験紙を貼りつけて電解液の漏液の有無を確認した。
外装体の膨れが確認されたものについては図1におけるA-A’断面状態の観察を行った。
なお、治具で固定することで電池の厚さが変わらない状態で試験電池が10%以上膨れた場合、膨れにより溶着部分に負荷がかかり始めることを確認した。
また、70℃劣化試験では実施例1~10においては漏液が確認できなかったのに対し、比較例1においては3個、比較例2においては5個について漏液を確認した。
以下の実施例では、それぞれ、以下の個数の漏液を確認した。
実施例1は5個、実施例2は3個、実施例3は4個、実施例6は9個、実施例7は7個、実施例8は9個、比較例1は14個、比較例2は18個
また、アルミニウム層の露出はなかった。
また、実施例3~5、8~10において膨れを確認したものはいずれも図8のように界面接着部15に界面溶着剥離部16を形成していたが、アルミニウム層の露出はなかった。
これは、封止部や樹脂塊に一体化せずに接着している界面接着部15が存在しているものと考えられる。
前記接着部15は、加熱後の冷却までの時間が、熱溶着層や一体化して接着した凝集溶着部19より強度が小さいために、界面接着部15の端部が優先的に剥離するためであると考えられる。
加えて、界面接着部に接して樹脂塊が形成されているものについては樹脂塊中の面で剥離が止まっており、封止部にすら到達していないものも確認できた。
さらに、実施例2、4、5、7、9、10のように界面接着部に歪曲部を形成したものは、剥離距離は同じであるが、湾曲により界面接着層の距離が延びるため、それぞれ実施例1、3、6,8よりも界面接着部の接着力が大きなものとなる。
一方、漏液がないものは界面溶着剥離部が凝集溶着部まで達しておらず、アルミニウム層の露出はなかった。
実施例1~3と実施例6~8を比較すると、実施例6~8においては冷却までの間隔が長くなったことで熱溶着層の脆化が進んだものと考えられる。そして、脆化が進み、凝集接着面に達した場合に熱溶着層の亀裂が生じやすくなっているものと考えられる。
漏液数 膨れの有無 アルミニウム層の腐食
実施例1 0 7 0
実施例2 0 6 0
実施例3 0 5 0
実施例4 0 8 0
実施例5 0 6 0
実施例6 0 5 0
実施例7 0 6 0
実施例8 0 7 0
実施例9 0 6 0
実施例10 0 7 0
比較例1 3 11 3
比較例2 5 14 5
漏液数 膨れの有無 アルミニウム層の腐食
実施例1 5 20 5
実施例2 3 20 3
実施例3 4 20 4
実施例4 0 20 0
実施例5 0 20 0
実施例6 9 20 9
実施例7 7 20 7
実施例8 0 20 9
実施例9 0 20 0
実施例10 0 20 0
比較例1 14 20 14
比較例2 18 20 18
Claims (11)
- 正極と負極をセパレーターを介して対向した発電要素を、熱溶着層、バリア層、保護層を積層したフィルム状外装材内に収容し、
前記発電要素を収容したフィルム状外装材の周囲を封止した封止部を有するフィルム外装電池であって、
前記封止部に凝集溶着部と、前記凝集溶着部の発電要素収容部側に隣接してフィルム状外装材同士の接着界面を有する第一の界面接着部を有することを特徴とするフィルム外装電池。 - 前記第一の界面接着部の接着界面の少なくとも一部に湾曲部が形成されていることを特徴とする請求項1記載の1つに記載のフィルム外装電池。
- 前記発電要素収納部側の前記封止部の近傍に形成された樹脂塊とを有することを特徴とする請求項1または2記載のフィルム外装電池。
- 前記樹脂塊と前記封止部が一体化または隣接していることを特徴とする請求項4記載のフィルム外装電池。
- 前記樹脂塊の内部にフィルム状外装材同士の接着界面を有する第二の界面接着部を有することを特徴とする請求項3または4記載のフィルム外装電池。
- 前記第二の界面接着部に湾曲部が形成されていることを特徴とする請求項5記載のフィルム外装電池。
- 前記第一の界面接着部と前記第二の界面接着部とが連続していることを特徴とする請求項5または6のいずれか1項に記載のフィルム外装電池。
- 前記界面接着部の発電要素収納部側に一体に樹脂塊を形成したことを特徴とする請求項5から7のいずれか1項に記載のフィルム外装電池。
- 正極と負極をセパレーターを介して対向した発電要素を、溶着層、バリア層、保護層を積層したフィルム状外装材に収容して、前記フィルム状外装材の周囲を封止して封止部を形成したフィルム外装電池の製造方法であって、
前記封止部を両面から加熱部材を押し当てて加熱した後に、加熱部材を押し当てた部分から取り除き、冷却部材を前記加熱部材を押し当てた部分とともに隣接する発電要素収納部側の一部にも押し当てて冷却して、凝集溶着部と、前記凝集溶着部に隣接した界面接着部と、を形成することを特徴とするフィルム外装電池の製造方法。 - 前記の両面の加熱部材を、前記フィルム状外装材の面に対して対称に押し当てたことを特徴とする請求項9記載のフィルム外装電池の製造方法。
- 前記の両面の加熱部材の一方を、前記フィルム状外装材の面に対して他方よりも発電要素側に近づけて押し当てたことを特徴とする請求項9記載のフィルム外装電池の製造方法。
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JP2018515881A (ja) * | 2015-08-27 | 2018-06-14 | エルジー・ケム・リミテッド | 二次電池のシール装置 |
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Publication number | Publication date |
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CN104412407A (zh) | 2015-03-11 |
US20150325822A1 (en) | 2015-11-12 |
CN104412407B (zh) | 2018-04-10 |
JPWO2013191125A1 (ja) | 2016-05-26 |
US10510997B2 (en) | 2019-12-17 |
US9871231B2 (en) | 2018-01-16 |
US20180123091A1 (en) | 2018-05-03 |
CN108470857A (zh) | 2018-08-31 |
EP2863448A1 (en) | 2015-04-22 |
EP2863448A4 (en) | 2015-12-30 |
EP2863448B1 (en) | 2021-03-03 |
JP6183919B2 (ja) | 2017-08-23 |
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