Battery sealing piece and manufacturing method thereof

Abstract

The invention provides a battery sealing body and a manufacturing method thereof, which can improve manufacturing efficiency and inhibit generation of hydrogen fluoride in a battery. A battery sealing material in which a metal sealing member for sealing an opening of a battery container, a metal terminal member, and a gasket member interposed between the sealing member and the terminal member are integrated by a sealing member, the gasket member containing a first thermoplastic resin resistant to hydrogen fluoride, the sealing member contains a second thermoplastic resin, the sealing member has a substantially flat-plate-shaped main body portion and a hole portion provided through the main body portion in the thickness direction, and the pre-molded gasket member is sandwiched between the outer peripheral portion of the terminal member and the inner peripheral portion of the hole portion of the sealing member. The closing member is injection-molded in a state in which the closing member is in close contact with each of the terminal member, the gasket member, and the sealing member, and there is no space that is an air layer.

Description

Technical Field

[0001] The present invention relates to a battery sealing component and a manufacturing method thereof. Background Art

[0002] A rechargeable battery is used that has a bottomed square or cylindrical shape with an opening on one side. A sealing member is attached as a lid to seal the opening of the battery's casing. The sealing member has through-holes formed in it, and electrode terminals are provided to be inserted through the through-holes. The electrode terminals are connected to wires drawn from the battery interior, providing electrical communication between the interior and exterior of the battery. These sealing members and electrode terminals are typically attached to the opening of the battery casing with high sealing performance.

[0003] For example, Patent Document 1 discloses a battery case cover in which a cover plate having a cover through-hole and an electrode are covered with a retaining resin. Patent Document 1 describes a method of joining the cover plate and electrode using laser processing to form fine grooves, and then injecting resin into the cover plate and electrode in an insert molding machine to form the cover plate and electrode. This method achieves a single-piece formation of the cover plate and electrode with the retaining resin.

[0004] Patent Document 2 discloses a top cover assembly for a rechargeable battery in which electrode terminals are connected to a cover plate having an electrode extraction hole via a sealing ring (gasket). Patent Document 2 also describes a technique for connecting the electrode terminals to the cover plate using a fixing member composed of a metal retainer and an insulator, wherein the metal retainer is welded to the cover plate and the insulator covers the metal retainer. Prior art literature Patent Literature

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 2020-145173 Patent Document 2: Japanese Patent Application No. 2021-526707 Summary of the Invention Technical problem to be solved by the invention

[0006] In Patent Document 1, the electrodes are covered with a retaining resin to maintain airtightness between the retaining resin and the battery cover. However, since the retaining resin is directly exposed to the battery interior, the resin constituting the retaining resin or the filler contained in the retaining resin is subject to degradation by the hydrogen fluoride generated within the battery. Therefore, in a structure such as Patent Document 1, it is necessary to select a retaining resin or filler that is resistant to hydrogen fluoride. In this regard, nylon, the resin material exemplified in Patent Document 1, is not sufficient.

[0007] In addition, in Patent Document 2, a sealing ring as a gasket is provided between the electrode terminal and the cover plate to improve safety. Here, in the sealing member disclosed in Patent Document 2, generally, a fixing member is first made, and the fixing member is a molded product that is formed as a whole by injection molding an insulator covering the metal retainer with respect to the metal retainer by a sealing member made of a thermoplastic resin. Then, the fixing member is pressed into the cover plate in a manner covering these members from the upper side so as to clamp the gasket (sealing ring) between the electrode terminal and the cover plate, and then the metal retainer part of the fixing member is welded to the cover plate, thereby manufacturing the sealing member. In the above-mentioned manufacturing method, the manufacturing process of the fixing member and the welding process achieved by welding the metal retainer part of the fixing member to the cover plate are necessary. Therefore, there is a technical problem that the number of working hours increases and the production efficiency decreases. Furthermore, in the aforementioned manufacturing method, since the fixing member, a pre-molded product formed with a sealing member, is attached to the cover plate, an air layer may form between the molded product comprising the electrode terminal and sealing member and the gasket, or between the molded product comprising the electrode terminal and sealing member and the cover. In such cases, there is a technical problem that moisture remaining in the air layer may infiltrate the battery and mix with the electrolyte, thereby generating hydrogen fluoride within the battery. Therefore, similarly to Patent Document 1, there is a need to select a resin material or filler having resistance to hydrogen fluoride.

[0008] An object of the present invention is to provide a battery sealing member that can improve manufacturing efficiency and suppress the generation of hydrogen fluoride inside the battery. Technical solutions used to solve technical problems

[0009] That is, the gist of the present invention is as follows. (1) A battery sealing member, wherein a metal sealing member for sealing an opening of a battery container, a metal terminal member, and a gasket member interposed between the sealing member and the terminal member are integrated by a closure member, wherein: The gasket member contains a first thermoplastic resin having resistance to hydrogen fluoride, The closing member contains a second thermoplastic resin, The sealing member includes a substantially flat plate-shaped main body and a hole extending through the main body in a thickness direction. The preformed gasket member is sandwiched between the outer periphery of the terminal member and the inner periphery of the hole of the sealing member. The closing member is injection-molded in a state in which the closing member is in close contact with each of the terminal member, the gasket member, and the sealing member without any space serving as an air layer. (2) The battery sealing member according to (1), wherein the terminal member is arranged in a state where at least a portion of the terminal member is exposed on one main surface side of the sealing member. The closing member covers the outer peripheral portion of the terminal member, the gasket member, and the inner peripheral portion of the sealing member on the one main surface side. (3) The battery sealing member according to (1) or (2), wherein the lower end surface of the outer peripheral portion of the terminal member and the upper end surface of the inner peripheral portion of the hole portion of the sealing member are arranged opposite to each other with the gasket member interposed therebetween. (4) The battery sealing member according to (1) or (2), wherein the outer peripheral end surface of the outer peripheral portion of the terminal member and the inner peripheral end surface of the hole portion of the sealing member are arranged opposite to each other with the gasket member interposed therebetween. (5) The battery sealing member according to (3) is characterized in that the terminal member has a flange portion at the outer peripheral portion formed by extending from the side opposite to the side of the terminal member facing the sealing member toward the next step and protruding in the outer peripheral direction. The closing member is formed so as to cover the entire surface of the flange portion exposed toward the one main surface except for a portion in contact with the gasket member. (6) The battery sealing member according to (2) is characterized in that the terminal member has a flange portion or two or more flange portions at the peripheral portion, which is formed by extending downward from the surface of the one main surface of the terminal member by at least one step and projecting in the peripheral direction. At least one of the flange portions is arranged such that a stepped bottom surface of the flange portion and a lower end surface of an inner peripheral portion of the hole portion of the sealing member are opposed to each other with the gasket member interposed therebetween. (7) The battery sealing material according to (2), wherein the sealing member has a step portion that is one step downward at the inner peripheral portion on the one main surface side. (8) The battery sealing member according to (1) or (2), wherein the sealing member has a protrusion protruding in the thickness direction near the inner peripheral portion. The gasket member has a recessed portion recessed in the thickness direction, The gasket member is sandwiched in a state where the protrusion of the sealing member and the recess of the gasket member are closely fitted. (9) The battery sealing member according to (1) or (2), wherein the terminal member has a circumferential recessed portion recessed inward in the circumferential direction on the outer peripheral portion. The washer member has a recessed portion recessed circumferentially inward. The gasket member is sandwiched in a state where the inner peripheral end portion of the sealing member is fitted in close contact with the recessed portion of the gasket member and the gasket member is fitted in close contact with the recessed portion of the terminal member. (10) The battery sealing material according to (1) or (2), wherein the sealing member and the terminal member each have a bonding surface at the interface with the closing member, and a hydroxyl-containing coating film containing hydroxyl groups is formed on the bonding surface. (11) The battery sealing member as described in (10), characterized in that the hydroxyl-containing coating has a macro-concave-convex portion consisting of a plurality of concave-convex portions on its surface, and a fine concave-convex portion on the surface of the macro-concave-convex portion, wherein the opening diameter (D) of the concave-convex portion of the macro-concave-convex portion is 20 μm to 200 μm, the depth (L) is 20 μm to 200 μm, and the aspect ratio (L / D) of the opening diameter (D) to the depth (L) is 0.5 to 5, and the fine concave-convex portion has a plurality of openings of 10 nm to 50 nm and a thickness of 10 nm to 1000 nm, The sealing member and the terminal member are respectively joined to the closing member via the joining surface, with the closing member entering the macro-concave-convex portion and the fine-concave-convex portion. (12) A method for manufacturing a battery sealing member, wherein the battery sealing member is formed by integrating a metal sealing member for sealing an opening of a battery container, a metal terminal member, and a gasket member interposed between the sealing member and the terminal member through a sealing member. Its characteristics are: The gasket member contains a first thermoplastic resin having resistance to hydrogen fluoride, The closing member contains a second thermoplastic resin, The sealing member has a substantially flat plate-shaped main body and a hole extending through the main body in the thickness direction. The manufacturing method of the battery sealing member includes: a member preparation step of sandwiching the preformed gasket member between the outer peripheral portion of the terminal member and the inner peripheral portion of the hole portion of the sealing member; and An injection molding step of injection molding the closing member so as to be in close contact with each of the terminal member, the gasket member, and the sealing member without any space serving as an air layer. (13) The method for manufacturing a battery sealing member according to (12), wherein, in the member preparation step, the terminal member is arranged so that at least a portion thereof is exposed on one main surface side of the sealing member. In the injection molding step, the injection molding is performed so that the closing member covers the outer peripheral portion of the terminal member, the gasket member, and the inner peripheral portion of the sealing member on the one main surface side. (14) The method for manufacturing a battery sealing member according to (12) or (13), characterized in that it includes a coating forming step, wherein a laser treatment is performed to irradiate the surfaces of the sealing member and the terminal member with a laser, thereby forming a bonding surface on the surfaces of the sealing member and the terminal member, wherein a hydroxyl-containing coating containing a hydroxyl group is formed on the bonding surface. The member preparation step and the injection molding step are performed using the sealing member and the terminal member obtained in the coating film forming step. (15) The method for manufacturing a battery sealing member according to (14), characterized in that, in the coating forming step, the bonding surface is formed on the side of the one main surface for injection molding in the outer peripheral portion of the terminal member and the inner peripheral portion of the hole portion of the sealing member, respectively. In the member preparation step, the terminal member and the sealing member are arranged so that the joint surface formed on the terminal member and the joint surface formed on the sealing member are exposed toward the one main surface. In the injection molding step, the injection molding is performed so that the closing member covers the joining surface between the terminal member and the sealing member on the one main surface side. Effects of the Invention

[0010] According to the present invention, an object is to provide a battery sealing member that can improve manufacturing efficiency and suppress the generation of hydrogen fluoride inside the battery. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1 This is a schematic diagram showing the top surface shape of the battery sealing material according to the first embodiment of the present invention. Figure 2 This is a schematic diagram showing the bottom surface shape of the battery sealing material according to the first embodiment of the present invention. Figure 3 yes Figure 1 AA cross-sectional view is a schematic cross-sectional view of the battery sealing member according to embodiment 1 of the present invention. Figure 4 It is a schematic cross-sectional view showing the positional relationship between the gasket member and the sealing member when they are arranged in the first embodiment of the present invention. Figure 5 This is a schematic diagram showing an example of a method for obtaining the opening diameter (D) and depth (L) in the macro concavoconvex portion. Figure 6This is a schematic diagram showing the relationship between the laser beam diameter and the irradiation interval. Figure 7 It is a schematic cross-sectional view of a battery sealing member according to a second embodiment of the present invention. Figure 8 It is a schematic cross-sectional view showing the positional relationship between the gasket member and the sealing member when they are arranged in Embodiment 2 of the present invention. Figure 9 It is a schematic cross-sectional view of a battery sealing member according to a third embodiment of the present invention. Figure 10 It is a schematic cross-sectional view of a battery sealing member according to a fourth embodiment of the present invention. Figure 11 It is a schematic cross-sectional view showing the positional relationship between the gasket member and the sealing member when they are arranged in the fourth embodiment of the present invention. Figure 12 It is a schematic cross-sectional view of a battery sealing member according to a fifth embodiment of the present invention. Figure 13 It is a schematic cross-sectional view of a battery sealing member according to a sixth embodiment of the present invention. Figure 14 It is a schematic cross-sectional view showing the positional relationship among the terminal member, the gasket member, and the sealing member when they are arranged in the sixth embodiment of the present invention. DETAILED DESCRIPTION

[0012] The battery sealing member of the present invention and its manufacturing method are described in detail below. The present invention is not limited to the following embodiments and can be modified or combined in various ways without changing the scope of the present invention. In addition, in this specification and the accompanying drawings, components with substantially the same functions may be denoted by the same reference numerals to omit repeated description.

[0013] The battery sealing member of this embodiment is formed by integrating a metal sealing member that seals the opening of the battery container, a metal terminal member, and a gasket member sandwiched between the sealing member and the terminal member through a sealing member. Here, the gasket member contains a first thermoplastic resin that is resistant to hydrogen fluoride, and the sealing member contains a second thermoplastic resin. The sealing member has a generally flat main body and a hole portion that passes through the main body in the thickness direction. The pre-formed gasket member is sandwiched between the outer periphery of the terminal member and the inner periphery of the hole portion of the sealing member. The sealing member is injection molded in a state in which it is in close contact with each of the terminal member, the gasket member, and the sealing member without any space that becomes an air layer.

[0014] In addition, preferably, in the battery sealing member of the present embodiment, the terminal member is configured in a state where at least a portion is exposed to one main surface side of the sealing member, and the closing member covers the outer periphery of the terminal member, the gasket member, and the inner periphery of the sealing member on the one main surface side. Since the closing member is provided on one main surface side of the sealing member, when there is an electrolyte on the other side (the internal side of the battery), it is separated by the terminal member, the gasket member, and the sealing member, and the possibility of the closing member being exposed to the electrolyte can be avoided. In addition, on one main surface side of the sealing member, injection molding is performed from the one main surface side in a state where the terminal member is configured with the gasket member clamped therebetween, thereby making manufacturing (assembly and injection molding) easy, which is preferred.

[0015] Hereinafter, the battery sealing material of the present invention will be specifically described based on preferred embodiments 1 to 6.

[0016] [1. Implementation Method 1] [1-1. Battery sealing member] Figures 1 to 4 A battery sealing member 1 according to a first embodiment of the present invention is shown, wherein: Figure 1 It is a top view. Figure 2 This is a bottom view. Figure 3 yes Figure 1 AA cross-sectional view. Figure 4 These are partial cross-sectional views showing the placement of the gasket member 80 and the sealing member 20 during the manufacture of the battery sealing member 1. The battery sealing member 1 shown in these figures is used in either the positive or negative electrode, and only a portion of the sealing member for each electrode is shown. The size of each component can be appropriately modified depending on the size and shape of the opening of the battery being used. This also applies to the following embodiments 2 to 6.

[0017] Reference Figures 1 to 4 The battery sealing member 1 of the first embodiment comprises a sealing member 20, a terminal member 30, a gasket member 80 and a closing member 70. Figure 3 As can be seen, the gasket member 80 is sandwiched between the outer periphery of the terminal member 30 and the inner periphery of the sealing member 20. The terms "outer periphery" and "inner periphery" are not limited to the ends or side surfaces of the outer (or inner) periphery, but may broadly encompass the surrounding areas. Specifically, the "outer periphery" and "inner periphery" may encompass a large area including the ends or side surfaces of the ends, or may encompass an area slightly inward from the outer periphery or slightly outward from the inner periphery, excluding the ends.

[0018] These sealing member 20, terminal member 30 and gasket member 80 are integrated by the closing member 70. The closing member 70 is injection molded in a state where it is in close contact with each of the terminal member 30, gasket member 80 and sealing member 20 without any space forming an air layer. In addition, the closing member 70 is preferably joined to the terminal member 30, gasket member 80 and sealing member 20 respectively.

[0019] The so-called "space forming an air layer" refers to a space where air or water vapor or gas other than air can stay, and in the present invention, such a space is formed so as not to exist. If there is moisture in the air layer, hydrogen fluoride may be generated from the electrolyte in the electrolyte (for example, fluorine-containing compounds such as LiPF6) due to the moisture. Therefore, by forming the absence of an air layer, the generation of hydrogen fluoride can be prevented. In addition, regarding the absence of a space formed by an air layer, for example, by using an electron microscope such as SEM to observe the cross-section of the portion where the sealing member 70 is injection molded at a magnification of 50,000 times, it can be determined by confirming that there is no gap in the measurement field.

[0020] Since the resin material forming the closing member 70 is subjected to high temperature and high pressure during injection molding, the molten or plasticized resin material will come into contact with the terminal member 30, the gasket member 80 and the sealing member 20. At this time, the resin material flows into the interior of the fine concave-convex structure existing on the surface of each of the terminal member 30, the gasket member 80 and the sealing member 20. In addition, by solidifying the resin material, the closing member 70 is formed in a state where it exerts an anchoring effect on each of the terminal member 30, the gasket member 80 and the sealing member 20. In addition, the resin material is close to each of the terminal member 30, the gasket member 80 and the sealing member 20 to the extent that it can be bonded by the action of intermolecular forces such as hydrogen bonding or van der Waals force. In addition, by solidifying the resin material, the closing member 70 is formed in a state where it exerts intermolecular forces on each of the terminal member 30, the gasket member 80 and the sealing member 20. Furthermore, depending on the injection molding conditions and the materials used for the closing member 70 and the gasket member 80, the gasket member 80 that comes into contact with the injected resin material melts, and the resin material is fused with the gasket member 80. Furthermore, by solidifying the resin material and the gasket member 80, the closing member 70 is formed in a state of being integrated with the gasket member 80.

[0021] In this way, the closing member 70 is joined to each of the terminal member 30, the gasket member 80 and the sealing member 20 via at least one action selected from the group consisting of an anchoring effect, an intermolecular force and fusion accompanied by melting. As a result, the closing member 70 is in close contact with each of the terminal member 30, the gasket member 80 and the sealing member 20 without a space that becomes an air layer, which can prevent the generation of a leakage path. From the perspective of blocking the generation of the leakage path, at the interface between the closing member 70 and each of the terminal member 30, the gasket member 80 and the sealing member 20, it is preferred that at least one (one) continuous joint is provided in the form of a cross-section of the flow path between the inside and the outside of the battery through which the hole 26 passes, and it is more preferred that several (multiple) continuous joints are provided.

[0022] The sealing member 20 is a member for sealing the opening of the battery container (not shown). Figures 1 to 4 The structure shown is roughly flat (referred to as the main body), and has the main body and a hole portion 26 that passes through the main body in the thickness direction. The hole portion 26 has roughly the same shape as the outer periphery of the terminal member 30 when viewed from above. For example, when the terminal member 30 is roughly cylindrical and the outer periphery of the terminal member 20 is circular when viewed from above, the hole portion 26 is also circular. A protrusion 21 that protrudes in the thickness direction of the sealing member 20 may also be provided near the inner periphery of the hole portion 26. In the present embodiment, a protrusion 21 that protrudes toward one main surface side (the side outside the battery) is provided near the inner periphery of the hole portion 26. By having the protrusion 21, the setting and fitting state with the gasket member 80 can be improved.

[0023] The shape of the sealing member 20 can be modified appropriately depending on the shape of the battery opening, but is typically a rectangular or circular, generally flat plate (main body) with the aforementioned hole 26 formed in its center. The main body may be processed appropriately or additional components may be added as needed. For example, the sealing member 20 may have a shape in which legs inserted into the battery container extend downward from the main body (toward the other main surface (the battery interior)).

[0024] The sealing member 20 is made of metal. As metal, the copper material made of copper or copper alloy, the iron material made of iron or iron alloy, the aluminum material made of aluminum or aluminum alloy, etc., the raw material is not limited and can be determined based on the various physical properties such as strength, corrosion resistance, and processability required for the sealing of the battery. Usually, an oxide film is formed on the surface of these metal materials. The oxide film can be a natural oxide film formed naturally in the atmosphere, or it can be an anodic oxide film formed by anodic oxidation. In addition, it can also be a rolled oxide film formed by hot rolling.

[0025] The terminal member 30 is an electrode terminal for connecting to a lead wire drawn from the inside of the battery to connect the inside of the battery to the outside. The terminal member 30 is made of metal and the same metal material as above is used. Figures 1 to 3 As shown, the terminal member 30 has a cylindrical central portion and a first flange portion 31 extending from the central portion, and has a generally cylindrical shape as a whole. The terminal member 30 may have a shape other than this (roughly square columnar, roughly flat, etc.), or may have an expanded portion, a cutout portion, etc., such as the first flange portion 31, and can be appropriately changed depending on the battery used. In addition, the terminal member 30 is arranged to overlap with the protrusion 21 protruding toward one main surface near the inner periphery of the sealing member 20 when viewed from above, and in this embodiment 1, is configured to cover at least one hole portion 26.

[0026] The gasket member 80 is a preformed member. As a molding method, a well-known method such as stamping molding or injection molding can be used. The gasket member 80 is sandwiched between the sealing member 20 and the terminal member 30. The gasket member 80 has an annular shape with a space inside. The gasket member 80 has an annular portion corresponding to the outer periphery of the terminal member 30. The gasket member 80 can pass through the inner space portion surrounded by the annular portion of the gasket member 80 and reach the terminal member 30 from the other main surface side of the sealing member 20 in a state of being sandwiched between the sealing member 20 and the terminal member 30. In addition, the gasket member 80 has a shape corresponding to the inner periphery of the hole portion 26 of the sealing member 20. In a state of the gasket member 80 being sandwiched between the sealing member 20 and the terminal member 30, the inner space portion surrounded by the annular portion of the gasket member 80 becomes roughly consistent with the hole portion 26. For example, the terminal member 30 is generally cylindrical, with a circular outer periphery when viewed from above. If the hole 26 is circular, the gasket member 80 also has a circular ring shape when viewed from above. The gasket member 80 blocks the gap between the sealing member 20 and the terminal member 30, enhancing airtightness and watertightness. The gasket member 80 suppresses the effects of hydrogen fluoride generated from the electrolyte within the battery on the sealing member 70 and the filler contained therein.

[0027] Therefore, the gasket member 80 comprises a thermoplastic resin (first thermoplastic resin) that is resistant to hydrogen fluoride. Examples of the first thermoplastic resin include, but are not limited to, fluororesins such as tetrafluoroethylene (PTFE), perfluoroalkoxy (PFA), perfluoroethylene propylene copolymer (FEP), ethylene tetrafluoroethylene copolymer (ETFE), and polyvinylidene fluoride (PVDF); polyolefin resins such as polyethylene (PE) and polypropylene (PP); and polyphenylene sulfide (PPS). Fluororesins such as PTFE and PFA are preferred as the first thermoplastic resin due to their resistance to hydrogen fluoride.

[0028] The shape of the gasket member 80 is not limited to the shape shown in the figure, and the shape can be appropriately changed according to the shapes of the portions of the terminal member 30 and the sealing member 20 that come into contact therewith, the degree of close contact, and the like.

[0029] The sealing member 70 is a member that is formed by injection molding to cover the terminal member 30, the gasket member 80, and the sealing member 20 from one main surface (the battery exterior), thereby sealing and integrating these members. The shape of the sealing member 70 can be appropriately modified depending on the shapes of the other members to be integrated, etc., as long as it does not hinder the purpose of the present invention.

[0030] The sealing component 70 is constructed in a manner including a thermoplastic resin (a second thermoplastic resin). The second thermoplastic resin may be the same as or different from the first thermoplastic resin and is not limited thereto, but is preferably a resin that can easily enter the contact surface with the components by injection molding. The second thermoplastic resin is not necessarily resistant to hydrogen fluoride, but may also have resistance to hydrogen fluoride. As the second thermoplastic resin, for example, fluororesins such as PTFE, PFA, FEP, ETFE, and PVDF; polyolefin resins such as PE and PP; PPS, polyetheretherketone (PEEK), etc. can be preferably listed. In order to prevent the gasket component 80 from being deformed during injection molding, the second thermoplastic resin is preferably a thermoplastic resin with a lower heat resistance temperature than the first thermoplastic resin. As the second thermoplastic resin, from the viewpoint of injection moldability and resistance to hydrogen fluoride, PP or PPS is preferred, and from the viewpoint of injection moldability, resistance to hydrogen fluoride, and voltage resistance, PPS is more preferred.

[0031] In the present invention, by inserting the preformed gasket member 80 and then performing injection molding on the closing member 70 , the gasket member 80 and the closing member 70 can be combined and integrally molded even when the injection molding conditions for the gasket member 80 and the closing member 70 are different.

[0032] Furthermore, in order to improve mechanical strength and suppress volume changes, it is preferred to incorporate various fillers into the sealing member 70. Any known inorganic filler can be used as the filler, but for the purposes of the present invention, glass fillers (typically 30-70% by mass) are particularly preferred for pressure resistance and dimensional stability. When glass fillers are incorporated, since the glass is corroded by hydrogen fluoride, it is particularly important to configure the sealing member 70 so that it is in close contact with the other components without any air space in order to prevent hydrogen fluoride from being generated from the electrolyte as described above.

[0033] Regarding the specific structure of embodiment 1, Figure 3As shown, the sealing member 20 has a circular hole portion 26 that passes through the substantially flat main body portion. The sealing member 20 has a protrusion 21 protruding toward one main surface near the inner peripheral portion of the hole portion 26. In addition, the gasket member 80 is annular when viewed from above, and has: an inner peripheral portion, the inner peripheral portion forming a recess having an inner wall surface, the inner wall surface being in contact with the inner peripheral side surface of the protrusion 21, the front end surface of the protrusion 21 opposite to the terminal member 30, and the outer peripheral side surface of the protrusion 21; and an outer peripheral portion, the outer peripheral portion extending from the inner peripheral portion toward the outer peripheral direction and in contact with the upper surface on one main surface side of the planar portion of the sealing member. In this way, the sealing member 20 has a protrusion 21 protruding in the thickness direction near the inner peripheral portion, and the gasket member 80 has a recess 81 recessed in the thickness direction. In addition, as Figure 4 As shown, the gasket member 80 is sandwiched between the protrusion 21 of the sealing member 20 and the recess 81 of the gasket member 80 in a tightly fitted manner. This makes it easier to position the gasket member 80 relative to the sealing member 20 during assembly. In addition, it is easier to prevent the gasket member 80 from moving during injection molding.

[0034] Furthermore, the inner circumference of the gasket member 80, formed by the interlocking protrusion 21 and recess 81, is sandwiched between the lower surface (lower end surface; battery interior side) of the outer circumference of the terminal member 30 and the upper surface (upper end surface; battery exterior side) of the inner circumference of the hole 26 of the sealing member 20, which are positioned vertically opposite each other. In this first embodiment, the terminal member 30 is arranged so as not to enter the hole 26 of the sealing member 20. That is, the outer circumference of the terminal member 30, the gasket member 80, and the inner circumference of the hole 26 of the sealing member 20 are stacked sequentially from the top (battery exterior side). By arranging these components in the aforementioned stacking order, they are covered by the sealing member 70 on one main surface side (battery exterior side). Thus, as previously described, the sealing member 70 is separated from the other main surface side (battery interior side) of the sealing member 20 by the terminal member 30, the gasket member 80, and the sealing member 20, thereby preventing the sealing member 70 from being exposed to the electrolyte. Furthermore, since the closing member 70 is injection molded from one main surface side, manufacturing (assembly and injection molding) can be facilitated, which is preferable.

[0035] In addition, if Figure 3The terminal member 30 has a first flange portion 31 at its outer periphery, which is formed by facing the next step on the side opposite to the side of the terminal member 30 facing the sealing member 20 and protruding from the center toward the outer periphery. In other words, the terminal member 30 has a first flange portion 31 at its outer periphery, which is formed by facing the next step on the side of one main surface of the terminal member 30 and protruding from the center toward the outer periphery. By having the first flange portion 31, a first step portion 32 is formed, which is composed of a first step side surface 33 (32) as a side surface of the center portion and a first step bottom surface 34 (32) as an upper surface of the first flange portion 31. By having the first step portion 32 and the first flange portion 31 as described above, as described above, the terminal member 30 can be arranged in a stacked state relative to the gasket member 80 and the sealing member 20. In addition, by having the first step portion 32 and the first flange portion 31, the closing member 70 is tightly attached to the first step side 33 (32), the first step bottom 34 (32), the outer peripheral end surface (outer peripheral side) 35 of the first flange portion 31, the lower surface of the first flange portion 31, the gasket member 80, and the main body of the sealing member 20. That is, the closing member 70 is injection molded by covering the entire surface of the outer peripheral portion of the terminal member 30, except for the portion in contact with the gasket member 80, which is exposed to one main surface. Therefore, the airtightness and watertightness are high, and the bonding strength is high. Regarding the width of each side and bottom surface (the first step side 33 (32), the first step bottom 34 (32) and the outer peripheral end surface (outer peripheral side 35) of the first flange portion 31) in the first step portion 32 and the first flange portion 31, it can be appropriately changed according to its purpose, taking into account the shape of the terminal member 30, the degree of tightness (joining) with the closing member 70, etc. The same applies to the subsequent embodiments.

[0036] [1-2. Hydroxyl-containing film] Preferably, a hydroxyl-containing coating containing hydroxyl groups is formed in the interfaces of the sealing member 20 and the terminal member 30 to which the closing member 70 is in close contact (these members are respectively indicated as the bonding surface 27 and the bonding surface 36). The hydroxyl-containing coating has a "macro-concave-convex portion" in which concave portions and convex portions are continuously formed alternately on the macro level, and a "fine concave-convex portion" formed on the surface of the macro-concave-convex portion. In the case of having the bonding surface 27 and the bonding surface 36, the closing member 70 is respectively in close contact (bonded) with each bonding surface of the sealing member 20 and the terminal member 30 in a state of entering the macro-concave-convex portion and the fine concave-convex portion, so that sufficient bonding strength and airtightness can be expected. In addition, the bonding surface 27 and the bonding surface 36 are preferably as Figure 3Thus, the surfaces on one side of a main surface to be injection molded are formed in the sealing member 20 and the terminal member 30, respectively. In this embodiment, a bonding surface 36 is formed on the upper side (first step bottom surface 34 (32)) of the first flange portion 31 of the terminal member 30. In addition, a bonding surface 27 is formed near the inner peripheral side surface 25 of the hole portion 26 of the sealing member 20, in a portion closer to the outer peripheral direction than the position of the gasket member 80. The terminal member 30 is configured to be exposed to one main surface side, and a bonding surface 27 and a bonding surface 36 containing a hydroxyl-containing coating are formed on one main surface side covered by the sealing member 70, thereby expecting sufficient bonding strength and airtightness.

[0037] Such a hydroxyl-containing coating may contain, depending on the metals constituting the terminal member 30 or the sealing member 20, a hydroxide (metal hydroxide) of a metal constituting the metal substrate, such as aluminum hydroxide (Al(OH)3), aluminum hydroxide oxide (AlO(OH)), copper hydroxide (Cu(OH)2), ferrous (II) hydroxide (Fe(OH)2), ferric (III) hydroxide oxide (FeO(OH)), or a hydroxide oxide (metal hydroxide oxide) of a metal constituting each member. Furthermore, the hydroxyl-containing coating may contain, depending on the metals constituting each member, an oxide (metal oxide) of a metal constituting each member, such as aluminum oxide (Al2O3), cuprous (I) oxide (Cu2O), copper (II) oxide (CuO), ferrous oxide (FeO), ferrosoferric (II, III) oxide (Fe3O4), or ferric oxide (Fe2O3).

[0038] About the hydroxyl-containing film, for example, the hydroxyl groups present near the surface of each joint surface of the terminal member 30 and the sealing member 20 are detected by glow discharge optical emission spectrometry (GD-OES) to confirm. Specifically, first, using GD-OES, the luminescence intensity (V) of the main metal and the hydroxyl group constituting each component is measured relative to the thickness direction of each joint surface. Then, the detected amount of the main metal constituting each component is calculated according to the cumulative value (area) of the luminescence intensity derived from the main metal. In addition, the detected amount of hydroxyl is measured according to the cumulative value of the luminescence intensity derived from the hydroxyl group. In addition, the ratio of the detected amount of hydroxyl to the total amount of the detected amount of the main metal and the detected amount of hydroxyl is calculated as the hydroxyl presence rate. The peaks appearing at 281nm and 309nm in the emission spectrum obtained by GD-OES are set to peaks derived from hydroxyl groups. The determination of the luminescence intensity near the surface of each component performed by GD-OES is as long as the determination is performed from the surface to a depth of 200nm. Specifically, the range from the detection of the luminescence intensity of the elements and hydroxyl groups of the main metal constituting each component to the time required for 200nm of sputtering (Japanese: sputtering) corresponding to the element of the main metal is measured. This measurement range (time) can be determined by measuring the sputtering rate (μm / min) of a standard sample containing the main metal element as the measurement object in advance. By measuring the luminescence intensity using GD-OES, it is possible to detect not only the components present in the outermost layer of each component, but also the components present at a certain depth that contribute to the resin bonding with the sealing component 70 for evaluation.

[0039] The hydroxyl group presence ratio is preferably 4% or more, more preferably 5% or more, further preferably 6% or more, and particularly preferably 7% or more. Since the hydroxyl group presence ratio is above the lower limit, the number of hydroxyl groups present near the surface of each bonding surface of each component increases, and interaction with the functional groups contained in the resin of the sealing component 70 can be expected. Furthermore, the bonding strength and airtightness of the sealing component 70 tend to be improved. The upper limit of the hydroxyl group presence ratio is not particularly limited, but is preferably 70% or less, more preferably 50% or less, further preferably 40% or less, and particularly preferably 30% or less. The hydroxyl group presence ratio varies depending on the method of forming the hydroxyl groups. For example, the hydroxyl group presence ratio tends to be higher when the components undergo wet treatment such as hydrated oxide treatment, chemical conversion treatment, or zincate treatment using warm or hot water, compared to when the components undergo laser treatment. When a hydroxyl-containing coating is formed by laser treatment, the hydroxyl group presence ratio is preferably 30% or less, more preferably 20% or less, further preferably 15% or less, and particularly preferably 10% or less.

[0040] On the surface of each joining surface of each component, a deposit formed by the accumulation of metal oxides formed by laser irradiation around the irradiated portion is formed into a film-like shape. The molten metal layer composed of such a deposit contains oxygen as the metal oxide as described above. The molten metal layer has a hydroxyl-containing film having hydroxyl groups on the outermost layer. In the present invention, as mentioned above, it is preferred that the entire surface of each joining surface is covered with a hydroxyl-containing film having macro-concave and convex portions and fine concave and convex portions. The so-called "entire joining surface" is not necessarily limited to 100% of the surface area of ​​each joining surface of the joining surface 27 or the joining surface 36, and does not exclude the situation where the surface not covered by the hydroxyl-containing film exists in the form of extremely small points due to the non-irradiated portion. Each joining surface can also be preferably covered by a hydroxyl-containing film by more than 90%, more preferably more than 95%.

[0041] <Macro concave and convex parts> The macro-concave-convex portion is a structure having a concave-convex shape of μm size, which is formed on the surface of the hydroxyl-containing coating. The macro-concave-convex portion has a structure consisting of a concave portion and a convex portion, wherein the concave portion is generated by perforating the metal substrate by receiving laser irradiation, and the convex portion is composed of a deposit of metal oxide generated by laser irradiation. Then, it has a repeated structure consisting of concave portions and convex portions by performing multiple laser irradiations adjacent to each other. The macro-concave-convex portion can be confirmed by observing the surface or cross-section of the bonding surface using, for example, a scanning electron microscope (SEM).

[0042] The macro-concave and convex parts preferably have a reference Figure 5The predetermined opening diameter (D) and depth (L) are obtained by the steps described above. The macro-concave-convex portion contains a metal hydroxide or a metal hydroxide oxide in the same manner as the hydroxyl-containing film. Alternatively, the macro-concave-convex portion may contain a metal oxide in the same manner as the hydroxyl-containing film.

[0043] Here, to calculate the opening diameter (D) and depth (L), a SEM is used to observe the cross-section of each of the terminal member 30 or the sealing member 20, or the sealing member 70 and each member in a state of close contact (joining). A cross-sectional photograph of a plurality of concave and convex portions formed by laser irradiation, consisting of at least twelve concave portions and eleven convex portions arranged alternately and continuously, is taken. The opening diameter (D) and depth (L) can be calculated based on the plurality of concave and convex portions included in the cross-sectional photograph.

[0044] Specifically, if Figure 5 As shown, after obtaining a cross-sectional photograph, the following lines are set to obtain it. Figure 5 This is an example of a diagram schematically showing a cross section that can be used to calculate the opening diameter (D) and depth (L) of the macro concavoconvex portion. Figure 5 This diagram assumes a case where a resin molded body 12 corresponding to the closing member 70 is joined to a metal member 11 corresponding to either the terminal member 30 or the sealing member 20 having macro-concave and convex portions formed thereon.

[0045] First, in Figure 5 For each of the twelve randomly selected consecutive concave portions, the deepest portion of the deepest bottom portion of each concave portion is defined as the lowest concave portion Pb1. A reference line RL1 is drawn, passing through the lowest concave portion Pb1 or a position lower than the lowest concave portion Pb1 and passing through the position where the sum of the distances from the lowest positions of each concave portion is minimized. Next, the highest convex portion of each convex portion sandwiched between the twelve concave portions is defined as the highest convex portion Pt1. A reference line RL2 is drawn, passing through the highest convex portion Pt1 and parallel to the reference line RL1. By drawing reference lines RL1 and RL2 through the lowest concave portion Pb1 and the highest convex portion Pt1, respectively, this prevents the depth L from being calculated as being larger or smaller than its intended value, thereby preventing the aspect ratio (L / D) from being calculated as being larger or smaller than it should be. Next, for the twelve consecutive concave portions including the bottom concave portion Pb1, twelve straight lines are drawn from the bottom of each concave portion in a direction perpendicular to the reference line RL2, and these straight lines are successively designated as lines a to l (in Figure 5 (indicated by dotted lines).

[0046] Regarding the above lines a to l, draw parallel median lines in the middle of adjacent lines, and sequentially designate these median lines as lines A to K. The interval between lines A and B can be set to the opening diameter D1 of the concave portion sandwiched by lines A and B and through which line b passes. Similarly, the intervals between adjacent lines among lines A to K can be set to opening diameters D1 to D10. In addition, for each of lines b to k, the distance from the bottommost part of each concave portion to the reference line RL2 can be set to the depths L1 to L10 of the ten concave portions. The opening diameters D1 to D10 and the depths L1 to L10 respectively correspond to the opening diameters D and depths L of the ten concave portions through which lines b to k among lines a to l pass, excluding the outermost lines a and l.

[0047] Thus, regarding Figure 5 the ten concave portions through which each of lines b to k included in Figure 5 pass, the depths L1 to L10 and the opening diameters D1 to D10 can be obtained. In addition, from the depths L1 to L10 and the opening diameters D1 to D10, the deviation values are detected using the Smirnov - Grubbs test (Japanese: スミルノフ·グラブス検定). To detect the deviation values, first, regarding the ten concave portions with depths L1 to L10, calculate the absolute deviation obtained by subtracting the average value of the depths L from each depth L value, and calculate the test statistic t by dividing the calculated absolute deviation by the unbiased standard deviation of the depths L1 to L10. Then, obtain the p - value representing the accuracy rate at which the test statistic t becomes this value. Next, consider the case where the p - value is less than 5% as a deviation value for detection. When a deviation value is detected, exclude the depth L of the concave portion with the detected deviation value from the ten concave portions with depths L1 to L10, and re - detect the deviation values for the depths L of the remaining concave portions, and then repeat the above operation until no deviation value is detected. Similarly, the deviation values are also detected based on the opening diameters D1 to D10. In addition, regarding

[0048] In addition, regarding Figure 5For each of the ten concave portions that lines b through k pass through, the aspect ratio (L / D) of each concave portion is calculated based on the depth L and opening diameter D of the remaining concave portions, excluding those where deviation values ​​are detected based on either or both of the depth L and opening diameter D. The depth L of each concave portion is divided by the opening diameter D of each concave portion. Furthermore, the average aspect ratio (L / D) of the multiple concave portions is calculated based on the individual aspect ratios (L / D). The average aspect ratio (L / D) obtained in this manner is defined as the aspect ratio (L / D) of the macro-concave-convex portion.

[0049] The opening diameter (D) is generally 20 μm to 200 μm, preferably 40 μm to 180 μm, more preferably 60 μm to 150 μm, and even more preferably 80 μm to 120 μm. When the opening diameter (D) is greater than the lower limit, the recess becomes larger, and therefore, the resin of the joined sealing member 70 easily enters the recess, or it is easy to satisfy the aspect ratio described later. On the other hand, when the opening diameter (D) is less than the upper limit, it is easy to achieve the fitting effect achieved by the entry of the resin, or it is easy to satisfy the aspect ratio described later.

[0050] The depth (L) is usually 20μm to 200μm, preferably 40μm to 180μm, more preferably 60μm to 150μm, and further preferably 80μm to 120μm. When the depth (L) is above the above lower limit, due to the sufficient depth, it is easy to exert the interlocking effect achieved by the entry of the resin, or it is easy to satisfy the aspect ratio described later. On the other hand, when the depth (L) is below the above upper limit, the formation of a coarse concave-convex structure caused by the increase in the depth (L) value and the opening diameter (D) is prevented, and it is easy to exert the interlocking effect achieved by the entry of the resin, or it is easy to satisfy the aspect ratio described later.

[0051] In addition, the aspect ratio (L / D) of the opening diameter (D) to the depth (L) is generally 0.5 to 5, preferably 0.5 to 4, more preferably 0.7 to 3, and even more preferably 1 to 2. By satisfying such an aspect ratio, the occurrence of gaps between the macro-concave and convex parts and the resin caused by the resin flowing into the deep part of the concave part can be suppressed, and the entire surface of the hydroxyl-containing coating can be sealed. In this way, the shape of the concave part is fully utilized to form the fitting of the terminal member 30 or the sealing member 20 and the resin of the sealing member 70 across the macro-concave and convex part, thereby improving their bonding strength and airtightness. When L / D is greater than the above lower limit, it becomes a size that is relatively too small in depth relative to the opening diameter of the concave part, and forms a shape with a moderate depth of the concave part, which makes it easy to form a shape in which the fitting of each member and the resin is utilized when the resin flows into the concave part. In addition, the aspect ratio is smaller than the above-mentioned upper limit value, thereby becoming a dimension that is relatively too large in depth relative to the opening diameter of the recess, and forming a roughly triangular shape in which the width of the recess gradually narrows from the opening to the deep part, so that the resin can easily flow into the deep part of the recess.

[0052] <Micro-concave and convex parts> Fine irregularities are structures with nanometer-sized irregularities that are formed on top of the macroscopic irregularities on the surface of the hydroxyl-containing coating. These irregularities are formed on the surface of the hydroxyl-containing coating when the molten metal layer containing the hydroxyl-containing coating is formed by laser irradiation. These irregularities can be confirmed, for example, by observing the surface or cross-section of a metal component using a scanning electron microscope.

[0053] The fine concavo-convex portion has nano-sized openings of 10 nm to 50 nm and a microstructure with a thickness of 10 nm to 1000 nm. When observed using a SEM, the fine concavo-convex portion appears as a sponge-like structure with fine openings of the aforementioned size. Like the hydroxyl-containing coating, the fine concavo-convex portion contains a metal hydroxide or metal hydroxide oxide. Alternatively, the fine concavo-convex portion may contain a metal oxide, similar to the hydroxyl-containing coating.

[0054] [1-3. Method for Manufacturing Battery Sealing Member] The manufacturing method of the battery sealing member 1 of the present invention includes a component preparation step in which a preformed gasket member 80 is sandwiched between the outer periphery of the terminal member 30 and the inner periphery of the hole 26 of the sealing member 20. The component preparation step includes the steps of separately preparing the terminal member 30, the sealing member 20, and the gasket member 80. Furthermore, the manufacturing method of the battery sealing member 1 of the present invention includes an injection molding step in which the closure member 70 is injection molded with the terminal member 30, the gasket member 80, and the sealing member 20 prepared in the component preparation step in close contact. Furthermore, the manufacturing method of the battery sealing member 1 of the present invention may also include a coating formation step in which a laser treatment is performed to irradiate the surfaces of the terminal member 30 and the sealing member 20 with a laser to form a bonding surface on each surface. The bonding surface is formed with a hydroxyl-containing coating containing hydroxyl groups. Alternatively, the component preparation step and the injection molding step may be performed using the sealing member 20 and the terminal member 30 obtained after the coating formation step.

[0055] <Component preparation process> In the component preparation process, first, the sealing member 20, the terminal member 30 and the gasket member 80 are formed and processed into predetermined shapes by a molding method and a processing method suitable for the metal or resin material of each of the sealing member 20, the terminal member 30 and the gasket member 80. Then, the prepared sealing member 20, the terminal member 30 and the gasket member 80 are used to form Figure 3 In the stacked state shown in FIG, the gasket member 80 is sandwiched between the outer periphery of the terminal member 30 and the inner periphery of the hole portion 26 of the sealing member 20. At this time, at least a portion of the terminal member 30 is configured to be exposed to one main surface side of the sealing member 20. In addition, the components are appropriately configured in such a way that the closing member 70 to be molded in the subsequent injection molding process does not enter and does not create a space that becomes an air layer. In addition, in order to prevent hydrogen fluoride that may be generated from the electrolyte on the other main surface side (inside the battery) from coming into contact with the molded closing member 70, the gasket member 80 is appropriately sandwiched between these components in such a way that the closing member 70 is separated by the sealing member 20 and the terminal member 30.

[0056] <Injection molding process> In the injection molding process, first, the sealing member 20, the terminal member 30 and the gasket member 80 prepared or arranged in the component preparation process are set in the mold for injection molding. Next, the second thermoplastic resin used in the sealing member 70 and the resin material containing filler as needed are melted to prepare the resin material for injection molding. Then, in the state where the various components are set, the resin material is injection molded from one main surface side (the side outside the battery) and made to flow into the cavity of the mold to form the shape of the specified sealing member 70. The injection molding conditions can appropriately set the resin temperature, mold temperature, etc. according to the resin material containing the second thermoplastic resin to be used. After the injection molding process, a cooling / solidification process is performed to cool the molten or plasticized resin material while applying pressure. After that, there is a removal process, in which the injection molding mold is opened and the battery sealing member 1 as a molded product is removed.

[0057] Through the above injection molding process, such as Figure 3 As shown, on the one main surface side, the closing member 70 is injection molded to cover the outer periphery of the terminal member 30, the gasket member 80 and the inner periphery of the sealing member 20, and the terminal member 30, the gasket member 80 and the sealing member 20 are integrated in a close-fitting state. In addition, preferably, the closing member 70 is integrated in a state of being respectively engaged with each of the terminal member 30, the gasket member 80 and the sealing member 20. That is, the closing member 70 is injection molded in a manner that covers the entire surface of the outer periphery of the terminal member 30 except the portion in contact with the gasket member 80 that is exposed to the one main surface side, so that the airtightness and watertightness are high, and the bonding strength is high. In addition, manufacturing (assembly and injection molding) becomes easy.

[0058] <Film Formation Process> In the film forming step, before the components are arranged in the component preparation step, the surfaces of the prepared sealing member 20 and terminal member 30 at the locations that can be in close contact with (joined to) the closing member 70 are subjected to a laser irradiation treatment (hereinafter referred to as "laser treatment"). The laser treatment forms the joint surfaces 27 and 36 of the sealing member 20 and terminal member 30 that are joined to the closing member 70. In addition, the joint surfaces 27 and 36 are formed by the laser treatment, and the joint surfaces 27 and 36 are formed with a hydroxyl-containing film.

[0059] That is, when forming the bonding surface 27 and the bonding surface 36 at the predetermined positions of each of the sealing member 20 and the terminal member 30, the bonding surface 27 and the bonding surface 36 are formed by laser processing on the surface of the outer peripheral portion of the terminal member 30 (for example, the bottom surface 34 (32) of the first step) and the inner peripheral portion of the sealing member 20 on the side of one main surface to be injection-molded (the battery exterior side). In addition, in the component preparation process, the terminal member 30 and the sealing member 20 are arranged in such a manner that the bonding surface 36 formed on the terminal member 30 and the bonding surface 27 formed on the sealing member 20 are exposed on one main surface side. Then, preferably, in the injection molding process, the resin of the sealing member 70 is injection-molded on one main surface side so as to cover the bonding surface 36 of the resin terminal member 30 and the bonding surface 27 of the sealing member 20. In this way, the bonding surface 27 and the bonding surface 36 having the hydroxyl-containing coating are formed on the one main surface side covered by the sealing member 70, thereby expecting sufficient bonding strength and airtightness. In addition, by performing laser processing on only one main surface side to form the joint surface 27 and the joint surface 36 that can be expected to exhibit sufficient joint strength and airtightness, there is no need to perform laser processing on the entire portion of the terminal member 30 and the sealing member 20 that contacts the closing member 70. Therefore, the time required for laser processing can be shortened and production efficiency can be improved.

[0060] As the laser, a known laser can be used, but since it is suitable for processing each component in a point shape as in the present invention, it is preferable to use a pulsed laser, for example, YAG laser, YVO4 laser, semiconductor laser, or fiber laser.

[0061] The formation principle of the hydroxyl-containing film is roughly as follows. That is, the energy of laser irradiation causes the various metal components to melt / evaporate, but due to evaporation and perforation, the space becomes the base of the concave portion, and the parts on both sides (adjacent sides) of the concave portion that are not irradiated with the laser become the base of the convex portion. At the same time, part or all of the molten metal part is oxidized to become metal oxide, and the convex portion is formed due to the accumulation of metal oxide around the irradiated portion that becomes the concave portion. The deposit composed of metal oxide covers the concave and convex portions to form a film-like shape. A metal molten layer having a concave-convex shape that configures a macroscopic concave-convex portion is formed by the deposit composed of metal oxide formed in the above manner. In addition, the metal oxide has at least some local ionicity, and there are metal ions (Al 3+ ) and oxide ions (O 2- Due to its electrostatic neutrality, the metal oxides present on the surface of the molten metal layer react with moisture in the air, causing them to hydroxylate, and the surface of the molten metal layer is covered with hydroxyl groups. Thus, a hydroxyl-containing film containing hydroxyl groups is formed on the outermost layer of the molten metal layer.

[0062] In addition, in the case where there is a laser non-irradiated portion that has not been irradiated by the laser, there is no metal molten layer and no hydroxyl-containing coating in the laser non-irradiated portion. Usually, an oxide coating is formed on the laser non-irradiated portion. The laser non-irradiated portion is usually flat because it does not have macroscopic concave-convex parts. Therefore, if a resin or the like is bonded to this part, it is not possible to expect an increase in the bonding strength due to the mechanical bonding caused by the macroscopic concave-convex parts. In addition, since it is flat, it is also easy to produce gaps, and therefore, it is also impossible to expect an increase in airtightness. Therefore, when there is a laser non-irradiated portion remaining on the bonding surface and no hydroxyl-containing coating is formed on the entire bonding surface, the airtightness and bonding strength in the bonding surface 27 and the bonding surface 36 may be reduced. In addition, since the above-mentioned hydroxyl-containing coating is not present in the laser non-irradiated portion, it is also impossible to expect the interaction brought about by the chemical bonding caused by the hydroxyl groups.

[0063] Laser treatment conditions In order to form a hydroxyl group-containing film having the above-described macro-concavoconvex portions and fine concavoconvex portions, it is preferable to set laser treatment conditions taking the following into consideration.

[0064] Laser processing is affected by the irradiation energy of the laser per unit area (hereinafter also referred to as "energy density"). Energy density indicates the laser output per unit area and per unit time received by the laser irradiated portion of the object (workpiece) to be processed by the laser. Energy density (J / mm 2 ) is expressed by the following formula (A1) based on the laser output W (W), the number of laser scans N (times), the laser irradiation interval C (mm), the laser scanning speed V (mm / s), the length Length perpendicular to the laser irradiation direction in the laser irradiated part, and the width Width parallel to the laser irradiation direction in the laser irradiated part. Energy density = (((Length × C) × Width × N) / V) × W) / (Length × Width) ... Formula (A1) By modifying the formula (A1), the following formula (A2) can be obtained: The energy density can be calculated by the formula (A2). Energy density = (W×N) / (C×V) ... Formula (A2)

[0065] The energy density is preferably 0.5 J / mm 2As the energy density increases, fine concave-convex portions having hydroxyl groups are easily formed on the surface of each metal component that has been subjected to laser treatment. In addition, a hydroxyl-containing film having a predetermined hydroxyl group presence ratio is easily formed. In addition, as the energy density increases, the concave portions of the macroscopic concave-convex portions to be formed are formed deeper, and the surface roughness after laser treatment tends to become larger. In addition, the higher the melting point of the metal constituting each metal component and the greater the thermal diffusion, the less likely it is to be affected by the laser. In view of the above, it is desirable to change the energy density according to the metal that is the object of laser treatment.

[0066] When laser processing is performed on various metal components mainly composed of aluminum, the energy density is preferably 0.5 J / mm 2 More than 1 J / mm 2 Above, more preferably 1.5 J / mm 2 In addition, when laser processing is performed on various metal components with aluminum as the main metal, the energy density is preferably 5 J / mm 2 Below, more preferably 4J / mm 2 Below, further preferably 3J / mm 2 the following.

[0067] When laser processing is performed on various metal components mainly composed of iron, the energy density is preferably 1 J / mm 2 More than, more preferably 2J / mm 2 Above, more preferably 3J / mm 2 In addition, when laser processing is performed on various metal components whose main metal is iron, the energy density is preferably 10 J / mm 2 Below, more preferably 8J / mm 2 Below, further preferably 6J / mm 2 the following.

[0068] When laser processing is performed on various metal components with copper as the main metal, the energy density is preferably 2 J / mm 2 More than 4 J / mm 2 Above, more preferably 6J / mm 2 In addition, when laser processing is performed on various metal components with copper as the main metal, the energy density is preferably 20 J / mm 2 Below, more preferably 15J / mm 2 Below, more preferably 10J / mm 2 the following.

[0069] By energy density being more than the above-mentioned lower limit, the surface of each component of the metal being subjected to laser treatment is easily formed with the fine concave-convex portion with hydroxyl group. In addition, the hydroxyl-containing coating with a prescribed hydroxyl presence rate is easily formed. Therefore, by having the fine concave-convex portion and the hydroxyl-containing coating, the airtightness and the bonding strength in the bonding surface 27 and the bonding surface 36 are easily improved. In addition, by energy density being more than the above-mentioned lower limit, the depth (L) of the concave portion of the macro-concave-convex portion to be formed is enlarged, and there is a tendency for aspect ratio (L / D) to become larger. Therefore, by making the resin of the enclosing member 70 enter the macro-concave-convex portion, to give play to the mechanical bonding (anchoring effect) of the macro-concave-convex portion and the enclosing member 70, thus, the bonding strength is easily improved. By energy density being below the above-mentioned upper limit, the depth (L) of the concave portion of the macro-concave-convex portion to be formed can be easily prevented from excessively becoming larger, and the aspect ratio (L / D) is excessively becoming larger. Therefore, the resin can penetrate deep into the concave portions of the macro-concave-convex structure, and by chemically bonding the hydroxyl groups of the metal components with the functional groups of the sealing member 70 throughout the entire macro-concave-convex structure, airtightness is easily improved. Furthermore, the convex portions of the macro-concave-convex structure can be prevented from having a slender, sharp structure, thereby suppressing a reduction in mechanical strength due to, for example, breakage of the convex portions. Furthermore, damage to the metal components can be prevented when the bonded portion breaks.

[0070] The laser conditions (laser processing conditions) in laser processing can be appropriately set to achieve the above-mentioned energy density. Parameters of laser processing conditions include laser output (W), laser frequency (kHz), laser beam diameter (μm), laser irradiation interval (μm), laser scanning speed (mm / s), and the number of laser scans (times). In addition, the number of scans refers to the number of times the laser is repeatedly irradiated along the same irradiation trajectory. Here, refer to Figure 6 , the relationship between the laser beam diameter and the irradiation interval is explained. The laser irradiation interval refers to the interval between the trajectory 13 of a laser irradiated on the object and the trajectory 13' of another laser irradiated adjacent to the laser. More specifically, the laser irradiation interval refers to the distance between the end of the trajectory 13 of the one laser on either side of the direction perpendicular to the scanning direction 14 and the end of the trajectory 13' of the other laser on the same side as the one laser. In the case of irradiating a pulsed laser, the laser trajectory is represented by a continuous trajectory of fine holes formed by each laser pulse. In this case, the laser irradiation interval 15 is equivalent to the length obtained by adding the width of the area clamped by the laser trajectory formed by the continuous fine holes to the size of the beam diameter 16. Table 1 shows examples of laser treatment conditions when the main metal of the metal substrate to be laser treated is aluminum, iron, or copper.

[0071] [Table 1]

[0072] [2. Implementation Method 2] Figure 7 This is a diagram showing a cross-sectional view of a battery sealing member 1 according to a second embodiment of the present invention.

[0073] like Figure 7 As shown, in the battery sealing member 1 of the second embodiment, the terminal member 30 is inserted into the hole 26 of the sealing member 20. As a result, the outer peripheral end surface (outer peripheral side surface) 35 of the outer peripheral portion (first flange portion 31) of the terminal member 30 and the inner peripheral end surface (inner peripheral side surface) 25 of the hole 26 of the sealing member 20 are arranged opposite to each other in a manner of sandwiching the gasket member 80. In addition, the upper surface (first step bottom surface 34 (32)) of the outer peripheral portion (first flange portion 31) of the terminal member 30, the upper surface of the gasket member 80, and a portion of the upper surface of the flat portion of the sealing member 20 arranged in the above manner are tightly attached and integrated by the sealing member 70 in a manner such that there is no space that becomes an air layer. In addition, in Embodiment 2, other parts are the same as those in Embodiment 1, and therefore, the same reference numerals are given to the same parts and their description is omitted.

[0074] Furthermore, by arranging the terminal member 30, the sealing member 20, and the gasket member 80 in this manner, these members can be arranged in a plane along the main body of the sealing member 20. This allows the battery sealing member to be relatively low in height, achieving a low profile.

[0075] In addition, the outer peripheral portion of the terminal member 30 arranged along the planar direction (the first step side surface 33 (32), the first step bottom surface 34 (32)), the gasket member 80 and the flat portion of the sealing member 20 that is closer to the outside than the gasket member 80 are covered by the closing member 70 and integrated. Therefore, the closing member 70 is arranged on one side of a main surface of the sealing member 20. Thus, when the electrolyte exists on the other side (the side inside the battery), it can be separated by the terminal member 30, the gasket member 80 and the sealing member 20, thereby avoiding the possibility of the closing member 70 being exposed to the electrolyte.

[0076] like Figure 7 、 Figure 8As shown, the gasket member 80 of the second embodiment is annular in shape when viewed from above and has: a middle portion 85 extending in the thickness direction; an inner peripheral portion that expands inwardly from the middle portion 85 and contacts the upper surface (first step bottom surface 34 (32)) of the first flange portion 31 of the terminal member 30; and an outer peripheral portion that expands inwardly from the middle portion 85 and forms a recessed portion 82 having an inner wall surface that surrounds the protrusion 21 of the inner peripheral portion of the sealing member 20 while contacting one main surface side of the flat portion (the battery exterior side). In this way, the sealing member 20 has a protrusion 21 protruding in the thickness direction near the inner peripheral portion, and the gasket member 80 has a recessed portion 82 recessed in the thickness direction. In addition, the gasket member is sandwiched in a state where the protrusion 21 of the sealing member 20 and the recessed portion 82 of the gasket member 80 are tightly fitted. This makes it easier to position the gasket member 80 relative to the sealing member 20 during assembly. Furthermore, it is easier to prevent the gasket member 80 from moving during injection molding.

[0077] Furthermore, the middle portion 85 of the gasket member 80 is sandwiched from the left and right by the outer peripheral end surface (outer peripheral side surface) 35 of the terminal member 30 and the inner peripheral end surface (inner peripheral side surface) 25 of the sealing member 20. Thus, since the terminal member 30, the gasket member 80, and the sealing member 20 are arranged in close contact in the planar direction, the possibility of the sealing member 70 being exposed to the electrolyte can be avoided as described above, and the sealing member 70 can be injection molded while the components are in close contact with each other.

[0078] In addition, at the interface where the sealing member 20 and the terminal member 30 are in close contact with the closing member 70, a bonding surface 27 and a bonding surface 36 having a hydroxyl-containing coating, macro-concave-convex portions and fine concave-convex portions are preferably formed, as in the first embodiment. In this embodiment, the bonding surface 36 is formed on the upper side (first step bottom surface 34 (32)) of the first flange portion 31 of the terminal member 30, which is closer to the inner circumference than the position of the gasket member 80. In addition, a bonding surface 27 is formed on the inner circumferential side surface (inner circumferential side surface) 25 of the hole portion 26 of the sealing member 20, which is closer to the outer circumference than the position of the gasket member 80. The bonding surface 27 and the bonding surface 36 can be formed by laser processing in the coating formation process as described in the first embodiment.

[0079] The manufacturing method of the battery sealing member of the second embodiment, similarly to the first embodiment, includes: a component preparation step in which the sealing member 20, the terminal member 30, and the gasket member 80 are prepared and arranged at predetermined positions; and an injection molding step, which, after the component preparation step, injection molds the resin of the sealing member 70 in a state where the resin is in close contact with each of the aforementioned components and the sealing member 70 without any air space between them. Furthermore, similarly to the first embodiment, a coating film forming step may be included before the component preparation step in which the bonding surfaces 27 and 36 are formed at predetermined positions on the sealing member 20 and the terminal member 30.

[0080] [3. Implementation Method 3] Figure 9 This is a diagram showing a cross-sectional view of a battery sealing member 1 according to a third embodiment of the present invention.

[0081] In the battery sealing member 1 of embodiment 3, the terminal member 30 of embodiment 2, which is located at the lower portion of the sealing member 20 (the entire lower surface of the main body and the first flange portion 31), passes through the hole portion 26 and penetrates toward the other main surface side (the battery interior side). That is, in embodiment 3, the terminal member 30 has a shape that protrudes toward both sides of the two main surfaces of the sealing member 20 at the upper and lower portions. Due to the shape of the terminal member 30 as described above, it is easy to achieve conduction with the components inside the battery through the portion of the terminal member 30 that passes through the sealing member 20. Figure 9 Although not shown in the figure, the lower portion of the terminal member 30 is generally cylindrical and extends toward the other main surface of the sealing member 20. However, the shape of the lower portion of the terminal member is not limited to this. For example, the lower portion of the terminal member 30 may extend in a plate-like, columnar, or hammer-like shape, or a portion of the lower portion of the terminal member 30 may extend. Furthermore, components within the battery may be connected to the lower portion extending in this manner to provide electrical continuity.

[0082] In the third embodiment, other parts are the same as those in the second embodiment, so the same reference numerals are given to the same parts and their description is omitted. The structure and the effects of the third embodiment other than the terminal member 30 are the same as those of the second embodiment.

[0083] [4. Implementation Method 4] Figure 10 This is a diagram showing a cross-sectional view of a battery sealing member 1 according to a fourth embodiment of the present invention.

[0084] like Figure 10As shown, in the battery sealing member 1 of the fourth embodiment, the terminal member 30 has, in addition to the first flange portion 31' corresponding to the first flange portion 31 in the first to third embodiments, a second flange portion 41 extending outwardly from the first flange portion 31' in the outer peripheral portion.

[0085] The first flange portion 31' forms a first step portion 32' consisting of a first step side surface 33' (32') as a side surface of the central portion and a first step bottom surface 34' (32') as an upper surface of the first flange portion 31'. Furthermore, the second flange portion 41 forms a second step portion 42 consisting of a second step side surface 43 (42) as a side surface of the first flange portion 31' and a second step bottom surface 44 (45) as an upper surface of the second flange portion 41.

[0086] The sealing member 20 has a flat plate-shaped planar portion and a protrusion 21 protruding toward the other main surface (toward the battery interior) around the hole 26 of the sealing member 20 .

[0087] The washer member 80 is arranged on the second step portion 42 formed by the second flange portion 41 of the terminal member 30. That is, the washer member 80 is arranged in close contact with a part or all of the second step side surface 43 (42) and the second step bottom surface 44 (42) in the second step portion 42 in a manner that covers a part or all of the second step portion 42. In addition, as Figure 11 Thus, the gasket member 80 has the recess 83 that matches the shape of the protrusion 21 of the sealing member 20 and into which the protrusion 21 is fitted.

[0088] Next, the sealing member 20 is placed on the gasket member 80 placed on the second step portion 42 formed by the second flange portion 41 of the terminal member 30. Figure 10 and Figure 11 As shown, the sealing member 20 is arranged so that the protrusion 21 is embedded in the predetermined recess 83 of the gasket member 80. At this time, the second step side surface 43 (42) as the outer peripheral end surface of the first flange portion 31' of the terminal member 30 and the inner peripheral end surface of the hole portion 26 of the sealing member 20 (at Figure 10 The inner peripheral side surface of the protrusion 21 is arranged opposite to each other in the left and right (horizontal direction) with the washer member 80 sandwiched therebetween. In addition, at this time, the second step bottom surface 44 (42) as the outer peripheral upper end surface of the second flange portion 41 of the terminal member 30 and the lower end surface (at the inner peripheral portion) of the hole portion 26 of the sealing member 20 are arranged opposite to each other. Figure 10 The middle portion is the lower surface of the inner peripheral portion of the hole portion 26 including the protrusion 21) and is arranged relative to each other in the up-down direction (thickness direction) so as to sandwich the washer member 80.

[0089] The gasket member 80 is annular in shape when viewed from above and comprises an outer peripheral portion that contacts the lower surface of the other main surface, located further outward from the protrusion 21 of the sealing member 20; and an inner peripheral portion that extends inward from the outer peripheral portion and forms a recessed portion 83 having an inner wall surface that contacts the outer peripheral side surface, the front end surface, and the inner peripheral side surface of the protrusion 21. Thus, the sealing member 20 has the protrusion 21 protruding in the thickness direction near the inner peripheral portion, and the gasket member 80 has the recessed portion 83 recessed in the thickness direction. Furthermore, the gasket member 80 is sandwiched between the protrusion 21 of the sealing member 20 and the recessed portion 83 of the gasket member 80, which fit snugly into each other. This facilitates positioning of the gasket member 80 within the sealing member 20 during assembly. Furthermore, movement of the gasket member 80 is easily prevented during injection molding.

[0090] Furthermore, the outer peripheral portion of the gasket member 80 is sandwiched from above and below by the second stepped bottom surface 44 (42) of the second flange portion 41 of the terminal member 30 and the lower end surface of the sealing member 20, which is located further outward than the protrusion 21. Furthermore, the vicinity of the front end surface of the protrusion 21 of the inner peripheral portion of the gasket member 80 is sandwiched from above and below by the second stepped bottom surface 44 (42) of the second flange portion 41 of the terminal member 30 and the front end surface of the protrusion 21 of the sealing member 20. Furthermore, a portion of the inner peripheral portion of the gasket member 80 is sandwiched from left and right (horizontally) by the second stepped side surface 43 (42) of the terminal member 30 and the protrusion 21 of the sealing member 20. This sandwiching portion allows the second flange portion 41 to act as a stopper when the internal pressure of the battery increases and presses the terminal member 30 toward the outside of the battery, thereby preventing the terminal member 30 from deviating from the battery container. In addition, by having this portion clamped from the left and right (horizontally), when the internal pressure of the voltage rises in the same manner and the terminal member 30 is squeezed toward the outside of the battery, the gasket member 80 sandwiched between the second flange portion 41 and the sealing member 20 can be squeezed to make the gasket member 80 tightly adhere to each of the terminal member 30 and the sealing member 20 to maintain airtightness.

[0091] In addition, by arranging the terminal member 30, the sealing member 20 and the gasket member 80 in the above-mentioned configuration at the periphery of the terminal member 30, the periphery of the terminal member 30 is configured so that the first flange portion 31' is inserted into the interior of the hole portion 26 of the sealing member 20, or the second flange portion 41 located below the first flange portion 31' is configured so as to protrude from the lower surface side of the hole portion 26 of the sealing member 20 toward the periphery on the inside of the battery.

[0092] The sealing member 70 is similarly formed by injection molding from one main surface side (battery exterior side) as in the first to third embodiments, so that the first step portion 32' (first step side surface 33' (32')) and the first step bottom surface 34' (32') of the terminal member 30, the gasket member 80 (the upper surface of the portion sandwiching the terminal member 30 and the sealing member 20 from the horizontal (left and right) direction), the inner peripheral portion of the hole portion 26 of the sealing member 20 (at the bottom of the battery exterior side) are arranged from the main surface side. Figure 10 The upper surface of the sealing member 70 is covered with the inner peripheral portion of the protrusion 21. The sealing member 70 is injection molded in a state of being in close contact with these components without leaving a space that becomes an air layer.

[0093] In addition, at the interface where the sealing member 20, the terminal member 30 and the closing member 70 are in close contact, it is preferable to form a bonding surface 27 and a bonding surface 36 having a hydroxyl-containing film, macro-concave and convex portions and fine-concave and convex portions, similarly to the first to third embodiments. Figure 10 As shown, the joint surface 36 is formed on the first stepped bottom surface 34' (32') of the first flange portion 31' of the terminal member 30. In addition, the joint surface 27 is formed on the upper surface of the inner peripheral portion of the hole portion 26 of the sealing member 20. As described above, the joint surface 27 and the joint surface 36 can be formed by laser processing in the film forming step.

[0094] The method for producing the battery sealing material of the fourth embodiment is carried out in the same manner as in the first to third embodiments.

[0095] [5. Implementation Method 5] Figure 12 This is a diagram showing a cross-sectional view of a battery sealing member 1 according to a fifth embodiment of the present invention.

[0096] like Figure 12 As shown, in the battery sealing member 1 of the fifth embodiment, the terminal member 30 has a first flange portion 31 ″ corresponding to the first flange portion 31 or 31 ′ of the first to fourth embodiments, and further has a second flange portion 41 ′ extending outwardly from the first flange portion 31 ″ in the outer peripheral portion.

[0097] In addition, by having the above-mentioned first flange portion 31" in the same manner as in embodiment 4, a first step portion 32" is formed which is composed of a first step side surface 33" (32") as the side surface of the central portion and a first step bottom surface 34" (32") as the upper surface of the first flange portion 31". In addition, by having a second flange portion 41', a second step portion 42' is formed which is composed of a second step side surface 43' (42') as the side surface of the first flange portion 31" and a second step bottom surface 44' (42') as the upper surface of the second flange portion 41', and a second flange portion side surface 45 is formed on the outer periphery.

[0098] The first flange portion 31″ in embodiment 5 preferably has a lower height of its second step side surface 43′ (42′). In addition, the height of the first step side surface 33″ (32″) is preferably lowered. By lowering their heights, the battery sealing member 1 can be made low-profile in cooperation with the configuration of the sealing member 20 described later. The height of the second step side surface 43′ (42′) is not limited, but for the purpose of achieving this low profile, the height of the first step bottom surface 34″ (32″) is preferably the same as the height of the upper surface of one main surface side (battery exterior side) of the sealing member 20 excluding the third step portion 22 described later. In addition, the height of the first step side surface 33″ (32″) is not limited, but for the purpose of achieving this low profile, the height of the upper surface of the terminal member 30 is preferably slightly higher than the upper surface of one main surface side of the sealing member 20 excluding the third step portion 22 described later.

[0099] In the fifth embodiment, the sealing member 20 is as follows Figure 12 The present invention is shown as comprising: a flat plate-shaped planar portion on the outer peripheral side; and a third step portion 22 formed by recessing the upper surface of one main surface of the planar portion (on the battery exterior side) around the hole portion 26 (on the inner peripheral side) of the sealing member 20. The third step portion 22 is formed by a third step side surface 23 (22) and a third step bottom surface 24 (22).

[0100] The gasket member 80 is annular in plan view and has an inner peripheral portion which is aligned with the lower surface of the sealing member 20 (at Figure 12and the outer peripheral portion, which descends from the inner peripheral portion in the thickness direction along the second flange portion side 45 of the terminal member 30. In addition, the gasket member 80 is arranged on the second step portion 42' formed by the second flange portion 41' of the terminal member 30. The corner formed by the second step bottom surface 44' (42') of the second flange portion 41' of the terminal member 30 and the second flange portion side 45 abuts against the inner angle formed by the inner peripheral portion and the outer peripheral portion of the gasket member 80, and the lower surface of the inner peripheral portion of the gasket member 80 abuts against the second step bottom surface 44' (42') of the terminal member 30, and the inner side surface of the outer peripheral portion of the gasket member 80 abuts against the second flange portion side 45 of the terminal member 30. That is, the washer member 80 is arranged in close contact along the second step side surface 43' (42'), the second step bottom surface 44' (42'), and a part or all of the second flange side surface 45, so as to cover a part or all of the second step portion 42' and a part or all of the second flange side surface 45, which is the outer peripheral portion of the second flange portion 41'. The corner formed by the second step bottom surface 44' (42') and the second flange side surface 45 of the second flange portion 41' of the terminal member 30 abuts against the inner corner formed by the inner and outer peripheral portions of the washer member 80, thereby facilitating the positioning of the washer member 80 relative to the terminal member 30 during assembly. In addition, it is easy to prevent the washer member 80 from moving during injection molding.

[0101] The sealing member 20 is arranged on the second step portion 42' formed by the second flange portion 41' of the terminal member 30 and the gasket member 80 arranged on the side surface 45 of the second flange portion. The sealing member 20 is arranged so that the upper surface of the gasket member 80 is in contact with the lower surface of the peripheral portion of the sealing member 20 where the third step portion 22 is formed. At this time, the surfaces of these members in contact are arranged in close contact. In addition, as Figure 12 As shown, the sealing member 20 is arranged so that a portion (gap) for the closure member 70 described later to enter is provided between the inner periphery of the hole portion 26 of the sealing member 20 and the second step side surface 43' (42') of the terminal member 30. That is, the closure member 70 enters the gap between the sealing member 20 and the terminal member 30, and forms a portion in close contact with the upper surface of the gasket member 80 exposed in the gap.

[0102] Thus, the second step bottom surface 44' (42') as the outer peripheral upper end surface of the second flange portion 41' of the terminal member 30 and the lower end surface (at the inner peripheral portion) of the hole portion 26 of the sealing member 20 are formed. Figure 12 The middle portion is the lower surface of the portion including the third step portion 22) and is arranged relative to each other in the up-down direction (thickness direction) so as to sandwich the washer member 80.

[0103] That is, the inner peripheral portion of the gasket member 80 is sandwiched from above and below by the second stepped bottom surface 44' (42') of the second flange portion 41' of the terminal member 30 and the lower end surface of the inner peripheral portion of the hole portion 26 in the sealing member 20, including the third stepped portion 22. This sandwiched portion allows the second flange portion 41' to act as a stopper when the internal pressure of the battery rises and presses the terminal member 30 toward the outside of the battery, thereby preventing the terminal member 30 from deviating from the battery container. Furthermore, if the battery rises and presses the terminal member 30 toward the outside of the battery, the gasket member 80 sandwiched between the second flange portion 41' and the sealing member 20 can be compressed, allowing the gasket member 80 to adhere tightly to each of the terminal member 30 and the sealing member 20, thereby maintaining airtightness.

[0104] In addition, by arranging the terminal member 30, the sealing member 20 and the gasket member 80 in the above-mentioned configuration at the periphery of the terminal member 30, the periphery of the terminal member 30 is configured so that the first flange portion 31" is inserted into the interior of the hole portion 26 of the sealing member 20, or the second flange portion 41' located below the first flange portion 31" is configured so as to protrude from the lower surface side of the hole portion 26 of the sealing member 20 toward the periphery on the inside of the battery.

[0105] The sealing member 70 is injection molded from one main surface side (the battery exterior side) in the same manner as in embodiments 1 to 4, so that the first step portion 32" (first step side surface 33" (32") and the first step bottom surface 34" (32") of the terminal member 30), the second step side surface 43' (42') as the side surface of the first flange portion 31", the upper surface of the gasket member 80 (the surface exposed to the gap generated between the terminal member 30 and the sealing member 20) and the inner peripheral portion of the hole portion 26 of the sealing member 10 (at the bottom of the battery exterior) are arranged from the main surface side. Figure 12 The upper surface of the sealing member 70 is covered with the third step portion 22 and the portion of the flat portion continuous from the third step portion 22. The sealing member 70 is injection molded in a state of close contact with these components without leaving any space that becomes an air layer.

[0106] In addition, at the interface where the sealing member 20, the terminal member 30 and the closing member 70 are in close contact, it is preferable to form a bonding surface 27 and a bonding surface 36 having a hydroxyl-containing film, macro-concave-convex portions and micro-concave-convex portions, similarly to the first to fourth embodiments. Figure 12 As shown, the bonding surface 36 is formed on the first step bottom surface 34 (32") of the first flange portion 31" of the terminal member 30. In addition, the bonding surface 27 is formed on the third step bottom surface 24 (22) of the third step portion 22 of the inner peripheral portion of the hole portion 26 of the sealing member 20. As described above, the bonding surface 27 and the bonding surface 36 can be formed by laser processing in the film forming step.

[0107] In embodiment 5, a low profile can be achieved by making the height of the first step side 33" (32") of the first step portion 32" relatively lower. At this time, as mentioned above, by providing the third step portion 22 on the sealing member 20, the amount of resin of the closing member 70 filled into the second step portion 42' and the third step portion 22 in order to seal the sealing member 20, the terminal member 30 and the gasket member 80 can be increased corresponding to the volume of the amount by which the thickness of the inner peripheral portion of the sealing member 20 is thinned due to the third step portion 22. Thus, even if the height of the first step side 33" (32") is lowered and the amount of resin of the closing member 70 injection-molded into the first step portion 32" is reduced, the amount of resin of the closing member 70 injection-molded between the third step portion 22 and the second step portion 42' can be made sufficient. In addition, thereby, the destructive strength of the base material can be improved, and in particular, the bonding strength between the closing member 70 and the terminal member 30 and the sealing member 20 can be improved.

[0108] The method for manufacturing the battery sealing material 1 of the fifth embodiment is carried out in the same manner as in the first to fourth embodiments.

[0109] [6. Implementation Method 6] Figure 13 This is a diagram showing a cross-sectional view of a battery sealing material 1 according to a sixth embodiment of the present invention.

[0110] like Figure 13 、 Figure 14 As shown, in the battery sealing member 1 of embodiment 6, the terminal member 30 has: a roughly cylindrical central portion; a circumferential protrusion 51, which is stepped down one step at the outer peripheral portion of the central portion and protrudes from the central portion toward the outer peripheral direction; and a circumferential recess 55, which is recessed downward from the circumferential protrusion 51 and further inward in the inner peripheral direction than the circumferential protrusion 51, or has a fifth flange portion 61 that protrudes from the circumferential recess 55 toward the outer peripheral direction.

[0111] In the sixth embodiment, the circumferential convex portion 51 is provided, thereby forming a fourth step portion 52 composed of a fourth step side surface 53 (52) as a side surface of the central portion and a fourth step bottom surface 54 (52) as an upper surface of the circumferential convex portion 51. Furthermore, the fifth flange portion 61 is provided from the circumferential concave portion, thereby forming a fifth step portion 62 composed of a fifth step side surface 63 (62) as a side surface of the circumferential concave portion 55 and a fifth step bottom surface 64 (62) as an upper surface of the fifth flange portion 61.

[0112] In the sixth embodiment, the sealing member 20 is as follows Figure 13 、 Figure 14The figure shows: a flat plane portion on the outer peripheral side; and a third step portion 22, wherein the third step portion 22 is formed by being recessed on the upper surface of one main surface side (battery exterior side) of the plane portion around the hole portion 26 of the sealing member 20 (inner peripheral side). The third step portion 22 is formed with a third step side surface 23 ( 22 ) and a third step bottom surface 24 ( 22 ). In addition, in embodiment 6, the third step portion 22 is not required, and the entire sealing member 20 may be formed into a flat plate shape. When the sealing member 20 is provided with the third step portion 22, the thickness of the inner peripheral end of the sealing member 20 can be reduced. Accordingly, the amount of resin filled into the second step portion 52 and the third step portion 22 of the sealing member 70 to seal the sealing member 20, the terminal member 30, and the gasket member 80 is increased by the volume corresponding to the amount of thickness reduction around the inner peripheral portion of the sealing member 20 due to the third step portion 22. This can improve the breaking strength of the base material, and in particular, can improve the bonding strength between the sealing member 70, the terminal member 30, and the sealing member 20. In addition, the height length of the circumferential recess 55 into which the inner peripheral end of the sealing member 20 is embedded through the gasket member 80 can be shortened, thereby achieving a low-profile battery sealing member 1.

[0113] In the sixth embodiment, the washer member 80 is configured to be embedded in the circumferential recess 55 of the terminal member 30. Figure 14 As shown, the washer member 80 is arranged in close contact along at least the lower surface of the circumferential protrusion 51 , the fifth step side surface 63 , and the fifth step bottom surface 64 .

[0114] Next, the sealing member 20 is placed on the gasket member 80. The sealing member 20 is placed so that the inner peripheral end of the hole 26 thereof is embedded from the outer peripheral side of the gasket member 80 to the circumferential inner side. Figure 13 、 Figure 14 As shown, the inner peripheral end portion of the third step portion 22 is arranged so as to fit into and cover the recess 84 of the gasket member 80 from the outer peripheral side of the gasket member 80. At this time, the sealing member 20 and the gasket member 80 are arranged in close contact.

[0115] The gasket member 80 is annular in plan view and has an outer peripheral portion that is aligned with the lower surface of the sealing member 20 (at Figure 13 and an inner peripheral portion, which expands from the outer peripheral portion toward the inner peripheral direction and rises in the thickness direction along the fifth step side 63 of the circumferential recess of the terminal member 30, and forms a recess 84 having an inner wall surface, which contacts the lower surface of the inner peripheral end of the sealing member 20 (at Figure 13In the middle, the lower surface of the inner peripheral end of the third step bottom surface 24 (22) is in contact with the upper surface of the inner peripheral side end surface and one main surface side (the battery external side). In addition, the outer peripheral portion of the gasket member 80 is clamped from above and below by the fifth step bottom surface 64 (62) in the terminal member 30 and the lower surface of the sealing member 20. In addition, the inner peripheral portion of the gasket member 80, which is formed by the inner peripheral end of the sealing member 20 and the recess 84 being fitted together, is clamped from left to right by the fifth step side surface 63 (62) of the terminal member 30 and the inner peripheral side end surface of the hole portion 26 of the sealing member 20, and is surrounded by the fifth step bottom surface 64 (62), the fifth step side surface 63 (62) and the lower end surface of the circumferential protrusion 51, and is embedded along the circumferential recess 55.

[0116] In other words, the fifth step side surface 63 (62) in the circumferential recess 55 of the terminal member 30 is arranged opposite to the inner circumferential end surface of the hole 26 of the sealing member 20, with the gasket member 80 sandwiched therebetween. Furthermore, the fifth step bottom surface 64 (62) of the terminal member 30 is arranged opposite to the lower end surface around the hole 26 of the sealing member 20, with the gasket member 80 sandwiched therebetween. By arranging the outer circumference of the terminal member 30, the inner circumference of the sealing member 20, and the gasket member 80 in the manner described above, when the internal pressure of the battery increases and the terminal member 30 is pressed toward the outside of the battery, the fifth flange portion 61 acts as a stopper, thereby preventing the terminal member 30 from deviating from the battery container. Furthermore, by applying pressure to the gasket member 80 sandwiched between the fifth flange portion 61 and the sealing member 20, the gasket member 80 can be brought into close contact with each of the terminal member 30 and the sealing member 20, maintaining airtightness.

[0117] As described above, the terminal member 30 has a circumferential recess 55 that is recessed circumferentially inward on its outer periphery. Furthermore, the gasket member 80 has a recess 84 that is recessed circumferentially inward. Next, the gasket member 80 covers the periphery of the inner circumferential end of the hole portion 26 of the sealing member 20, and the gasket member 80 is embedded in the circumferential protrusion 51 and the circumferential recess 55. That is, the gasket member 80 is sandwiched in a state where the inner circumferential end of the sealing member 20 and the recess 84 of the gasket member 80 are tightly fitted, and the gasket member 80 and the circumferential recess 50 of the terminal member are tightly fitted. Thus, during injection molding of the sealing member 70 or when the internal pressure of the battery rises, even if the terminal member 30 or the gasket member 80 is squeezed, the circumferential protrusion 51 can suppress deformation of the gasket member 80, thereby preventing the formation of space between the gasket member 80 and each of the terminal member 30 and the sealing member 20.

[0118] In addition, by making the terminal member 30, the sealing member 20 and the gasket member 80 into the above-mentioned configuration at the peripheral portion of the terminal member 30, the peripheral portion of the terminal member 30 is configured so that a portion of the circumferential recess 55 (fifth step side 63 (62)) is inserted into the interior of the hole portion 26 of the sealing member 20, or the fifth flange portion 61 located at a position further downward than the circumferential recess 55 is configured to protrude and extend from the lower surface side of the hole portion 26 of the sealing member 20 toward the peripheral direction on the internal side of the battery.

[0119] The sealing member 70 is similar to the first to fifth embodiments and is formed by injection molding from one main surface side (battery exterior side). Figure 13 As shown in FIG, the fourth step side surface 53 (52) of the terminal member 30, the fourth step bottom surface 54 (52), the outer peripheral side surface of the circumferential protrusion 51, the outer peripheral portion of the upper end surface of the gasket member 80 (the surface exposed to the outer peripheral side from the circumferential recess 55), the upper surface of the inner peripheral portion of the hole portion 26 of the sealing member 20 (at the Figure 13 The third step bottom surface 24 (22) is partially covered with the surface exposed to the outer peripheral side from the surface in contact with the gasket member 80. The closing member 70 is injection molded in a state of being in close contact with these members without any space forming an air layer.

[0120] In addition, at the interface where the sealing member 20, the terminal member 30 and the closing member 70 are in close contact, it is preferable to form a bonding surface 27 and a bonding surface 36 having a hydroxyl-containing film, macro-concave-convex portions and micro-concave-convex portions, similarly to the first to fifth embodiments. Figure 13 As shown, the joint surface 36 is formed on the fourth step bottom surface 54 (52) in the circumferential protrusion 51 of the terminal member 30. In addition, the joint surface 27 is formed on the upper surface of the inner peripheral portion of the hole portion 26 of the sealing member 20 (at Figure 13 The middle portion is a portion of the third step bottom surface 24 (22) exposed to the outer peripheral side from the surface in contact with the gasket member 80. As described above, the bonding surface 27 and the bonding surface 36 can be formed by laser processing in the film forming step.

[0121] The method for manufacturing the battery sealing material 1 of the sixth embodiment is carried out in the same manner as in the first to fifth embodiments.

[0122] [7. Effects] In the manufacturing process (assembly) of the battery, when the electrode terminal (terminal member 30) and the cover plate (sealing member 20) are sealed using a pre-formed resin sealing member 70, an air layer containing air is sometimes generated between the sealing member 70 and the electrode terminal and the cover plate due to the accuracy of the components and the assembly accuracy. When the air ambient gas under the manufacturing environment contains moisture, the moisture contained in the air ambient gas is sometimes enclosed inside the air layer of the sealing member. In this case, the moisture in the air layer reaches the electrolyte inside the battery, thereby generating hydrogen fluoride from the electrolyte, and the performance of the battery may be reduced. In addition, the sealing member 70 and the filler contained in the sealing member 70 are sometimes degraded by the generated hydrogen fluoride.

[0123] According to the present invention, the sealing member 70 is injection molded in close contact with the terminal member 30 , the gasket member 80 and the sealing member 20 without any air space, thereby preventing the generation of hydrogen fluoride from the electrolyte due to moisture contained in the air layer.

[0124] Furthermore, according to the present invention, the sealing member 70 is joined to each of the terminal member 30, the gasket member 80, and the sealing member 20, thereby preventing the generation of a leakage path between the sealing member 70 and each of the terminal member 30, the gasket member 80, and the sealing member 20. Thus, the inflow or outflow of gas or liquid through the leakage path between the outside and the inside of the battery can be prevented, thereby improving airtightness and watertightness.

[0125] Furthermore, even if moisture is mixed into the electrolyte during the manufacturing process of the battery and hydrogen fluoride is generated from the electrolyte, since the gasket member 80 is sandwiched between the sealing member 20 and the terminal member 30, the influence of the hydrogen fluoride generated from the electrolyte on the sealing member 70 and the filler contained in the sealing member 70 can be suppressed.

[0126] Furthermore, the present invention eliminates the need for a metal retainer as described in Patent Document 2, thereby reducing the number of components. Furthermore, the present invention eliminates the need for press-fitting and welding molded parts after preforming the metal retainer and the sealing member as described in Patent Document 2, thereby reducing assembly man-hours and improving manufacturing efficiency.

[0127] Furthermore, in the present invention, the preformed gasket member 80 is inserted and sandwiched between the terminal member 30 and the sealing member 20, and then the closure member 70 is injection molded. Thus, even if the injection molding conditions for the gasket member 80 (e.g., PFA) and the closure member 70 (e.g., PPS) differ, and the appropriate injection molding conditions for each resin cannot be met simultaneously (the resin melting temperature is 400°C or higher for PFA and 320°C or higher for PPS), the two can be combined and integrally molded.

[0128] In addition, in the present invention, it is preferred that a bonding surface 27 and a bonding surface 36 having a hydroxyl-containing coating, macro-concave and convex portions, and fine concave and convex portions are formed at the interfaces of the sealing member 20 and the terminal member 30 to which the closing member 70 is in close contact (bonded). As a result, the closing member 70 is in close contact (bonded) with each bonding surface of the sealing member 20 and the terminal member 30 in a state of entering the macro-concave and convex portions and the fine concave and convex portions, respectively, and therefore, sufficient bonding strength, airtightness, and watertightness can be expected.

[0129] Furthermore, in addition to the above-mentioned effects, the present invention also has more excellent effects as shown in the first to sixth embodiments. (Explanation of Symbols)

[0130] 1. Battery sealing parts; 11. Metal components; 12 resin molded body; 13, 13' laser trajectory; 14 scanning direction; 15. Laser irradiation interval; 16 beam diameter; 20 sealing member; 21 protrusion; 22 third step; 23 Side of the third step; 24 bottom surface of the third step; 25 inner peripheral end surface (inner peripheral side); 26 hole part; 27 joint surface; 30 terminal components; 31, 31', 31" first flange portion; 32, 32, 32” first step; 33, 33’, 33” side of first step; 34, 34’, 34” bottom of first step; 35 outer peripheral end surface (outer peripheral side surface); 36 joint surface; 41, 41' second flange portion; 42, 42', second step; 43, 43' Side of the second step; 44, 44', bottom of the second step; 45 side surface of the second flange portion; 51 circumferential convex portion; 52 fourth step; 53 Side of the fourth step; 54 bottom of the fourth step; 55 circumferential concave portion; 61 fifth flange portion; 62 fifth step; 63 Side of the fifth step; 64 bottom of the fifth step; 70 closure member; 80 washer member; 81, 82, 83, 84 recessed portion of the washer member; 85 The middle portion of the washer component.

Claims

1. A battery sealing member, wherein a metal sealing member for sealing an opening of a battery container, a metal terminal member, and a gasket member interposed between the sealing member and the terminal member are integrated with a closure member. It is characterized by: The gasket member contains a first thermoplastic resin having resistance to hydrogen fluoride, The closing member contains a second thermoplastic resin, The sealing member includes a substantially flat plate-shaped main body and a hole extending through the main body in a thickness direction. The preformed gasket member is sandwiched between the outer periphery of the terminal member and the inner periphery of the hole of the sealing member. The closing member is injection-molded in a state in which the closing member is in close contact with each of the terminal member, the gasket member, and the sealing member without any space serving as an air layer.

2. The battery sealing member according to claim 1, wherein: The terminal member is arranged in a state where at least a portion is exposed on one main surface side of the sealing member. The closing member covers the outer peripheral portion of the terminal member, the gasket member, and the inner peripheral portion of the sealing member on the one main surface side.

3. The battery sealing member according to claim 1 or 2, wherein: The lower end surface of the outer peripheral portion of the terminal member and the upper end surface of the inner peripheral portion of the hole portion of the sealing member are arranged to face each other with the gasket member interposed therebetween.

4. The battery sealing member according to claim 1 or 2, wherein: The outer peripheral end surface of the outer peripheral portion of the terminal member and the inner peripheral end surface of the hole portion of the sealing member are arranged to face each other with the gasket member interposed therebetween.

5. The battery sealing member according to claim 3, wherein: The terminal member has a flange portion at the outer periphery thereof, which is formed by extending downward from a surface of the terminal member opposite to the surface of the terminal member facing the sealing member and protruding in the outer periphery. The closing member is formed so as to cover the entire surface of the flange portion exposed toward the one main surface except for a portion in contact with the gasket member.

6. The battery sealing member according to claim 2, wherein: The terminal member has a flange portion or two or more flange portions at the outer periphery thereof, which is formed by facing downward at least one step on one side of the one main surface of the terminal member and protruding in the outer periphery direction. At least one of the flange portions is arranged such that a stepped bottom surface of the flange portion and a lower end surface of an inner peripheral portion of the hole portion of the sealing member are opposed to each other with the gasket member interposed therebetween.

7. The battery sealing member according to claim 2, wherein: The sealing member has a step portion that is one step lower at the inner peripheral portion on the one main surface side.

8. The battery sealing member according to claim 1 or 2, wherein: The sealing member has a protrusion protruding in the thickness direction near the inner peripheral portion. The gasket member has a recessed portion recessed in the thickness direction, The gasket member is sandwiched in a state where the protrusion of the sealing member and the recess of the gasket member are closely fitted.

9. The battery sealing member according to claim 1 or 2, wherein: The terminal member has a circumferential recessed portion on the outer periphery thereof, the recessed portion being recessed inward in the circumferential direction. The washer member has a recessed portion recessed circumferentially inward. The gasket member is sandwiched in a state where the inner peripheral end portion of the sealing member is fitted in close contact with the recessed portion of the gasket member and the gasket member is fitted in close contact with the recessed portion of the terminal member.

10. The battery sealing member according to claim 1 or 2, wherein: The sealing member and the terminal member each have a bonding surface at an interface with the closing member, and a hydroxyl-containing coating film containing hydroxyl groups is formed on the bonding surface.

11. The battery sealing member according to claim 10, wherein: The hydroxyl-containing coating has a macro-concave-convex portion consisting of a plurality of concave-convex portions on its surface, and a fine concave-convex portion on the surface of the macro-concave-convex portion, wherein the opening diameter (D) of the concave-convex portion of the macro-concave-convex portion is 20 μm to 200 μm, the depth (L) is 20 μm to 200 μm, and the aspect ratio (L / D) of the opening diameter (D) to the depth (L) is 0.5 to 5, and the fine concave-convex portion has a plurality of openings of 10 nm to 50 nm and a thickness of 10 nm to 1000 nm. The sealing member and the terminal member are respectively joined to the closing member via the joining surface, with the closing member entering the macro-concave-convex portion and the fine-concave-convex portion.

12. A method for manufacturing a battery sealing member, wherein the battery sealing member is formed by integrating a metal sealing member for sealing an opening of a battery container, a metal terminal member, and a gasket member interposed between the sealing member and the terminal member via a closure member. It is characterized by: The gasket member contains a first thermoplastic resin having resistance to hydrogen fluoride, The closing member contains a second thermoplastic resin, The sealing member has a substantially flat plate-shaped main body and a hole extending through the main body in the thickness direction. The manufacturing method of the battery sealing member includes: a member preparation step of sandwiching the preformed gasket member between the outer peripheral portion of the terminal member and the inner peripheral portion of the hole portion of the sealing member; and An injection molding step of injection molding the closing member so as to be in close contact with each of the terminal member, the gasket member, and the sealing member without any space serving as an air layer.

13. The method for manufacturing a battery sealing member according to claim 12, wherein: In the member preparation step, the terminal member is arranged in a state where at least a portion thereof is exposed on one main surface side of the sealing member. In the injection molding step, the injection molding is performed so that the closing member covers the outer peripheral portion of the terminal member, the gasket member, and the inner peripheral portion of the sealing member on the one main surface side.

14. The method for manufacturing a battery sealing member according to claim 12 or 13, wherein: The method comprises a coating forming step in which a laser treatment is performed to irradiate the surfaces of the sealing member and the terminal member with a laser so as to form a bonding surface on the surfaces of the sealing member and the terminal member, wherein a hydroxyl-containing coating is formed on the bonding surface. The member preparation step and the injection molding step are performed using the sealing member and the terminal member obtained in the coating film forming step.

15. The method for manufacturing a battery sealing member according to claim 14, wherein: In the coating forming step, the bonding surface is formed on the side of the one main surface for injection molding in the outer peripheral portion of the terminal member and the inner peripheral portion of the hole portion of the sealing member, respectively. In the member preparation step, the terminal member and the sealing member are arranged so that the joint surface formed on the terminal member and the joint surface formed on the sealing member are exposed toward the one main surface. In the injection molding step, the injection molding is performed so that the closing member covers the joining surface between the terminal member and the sealing member on the one main surface side.

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