JP6530847B1 - battery - Google Patents

Abstract

A battery that suppresses valve device damage to a battery element.
A battery device (400), a container and a valve device (200) are provided. The housing body is formed of a laminate and has an internal space in which the battery element is accommodated, and the first housing portion covering the internal space from the first side in the thickness direction of the battery, and the internal space in the thickness direction of the battery And a second receiving portion covering from the opposite second side. The valve device is attached to the housing, and the internal space of the housing can communicate with the external space. A peripheral edge joint 130 is formed in the housing by fusing the first housing portion and the second housing portion along the respective peripheral edge portions. The valve device is at least partially sandwiched between the first receiving portion and the second receiving portion at the peripheral joint. The first housing portion is disposed inward of the inner edge P2 of the peripheral joint, and has a bulging portion that bulges to the first side relative to the peripheral joint. The inner end 221 of the valve arrangement is located outside the outer edge P3 of the bulge.
[Selected figure] Figure 10A.

Description

  The present invention relates to a battery.

  Conventionally, a battery in which a battery element is accommodated in a container made of a laminate film is known (see, for example, Patent Document 1). The container of Patent Document 1 has a flange-like seal portion formed along the peripheral edge thereof, and a bulging portion which is disposed so as to be surrounded by the seal portion, and bulging from the seal portion The battery element is disposed inside the unit. Further, in the battery of Patent Document 1, a portion (hereinafter, referred to as an easy peeling portion) that is more easily peeled than the other portion is formed in the sealing portion. The easily peelable portion generates gas in the container, and preferentially peels when the pressure in the container rises, and the gas is released through the hole formed at the center of the easily peelable portion. Thereby, the gas can be discharged safely and reliably.

  Moreover, patent document 2 is disclosing the battery which accommodated the battery element in the bag-type accommodating body. The valve device is attached to the seal formed along the periphery of the bag-shaped container.

Unexamined-Japanese-Patent No. 2010-153841 JP, 2016-31934, A

  When degassing is performed by the easily peelable portion as in Patent Document 1, it may be difficult to accurately control the pressure for degassing. On the other hand, if the valve device is attached as in Patent Document 2, the control of the pressure for degassing becomes relatively easy, but the valve device attached to the seal portion is a battery element disposed in the container. There is a risk of injury.

  The present invention has been made to solve such a problem, and its object is to allow the valve device to damage the battery element while allowing accurate control of the pressure at which the gas device is vented. It is providing a battery that can be suppressed.

  A battery according to one aspect of the present invention comprises a battery element, a housing, and a valve device. The housing body is formed of a laminate, has an internal space for accommodating the battery element, and covers the internal space from the first side in the thickness direction of the battery, and the thickness of the battery in the internal space And a second receiving portion covering from a second side opposite to the first side in the direction. The valve device is attached to the housing and can communicate the internal space of the housing with the external space. The peripheral joint portion is formed on the housing body by fusing the first housing portion and the second housing portion along the respective peripheral edge portions. The valve device is at least partially sandwiched between the first receiving portion and the second receiving portion at the peripheral joint. The first housing portion is disposed inward of the inner edge of the peripheral edge joint, and has a bulging portion which bulges toward the first side in the thickness direction of the battery than the peripheral edge joint. The inner end of the valve arrangement is located outside the outer edge of the bulge.

  In the above battery, the inner end of the valve device may reach at least the inner edge of the peripheral joint.

  In the above battery, the inner end of the valve device may project from the inner edge of the peripheral joint toward the inner space.

  In the above battery, the inner edge of the peripheral junction is located in the vicinity of the valve device and on both sides of the first line along the extending direction of the first line intersecting the valve device and the inner edge of the peripheral junction. The first line may be located outside the second line and the third line, including the adjacent second line and the third line, respectively.

  In the above-described battery, the valve device includes a first portion in which a valve mechanism for discharging gas generated in the internal space of the container to the external space of the container is formed, and a valve mechanism for gas generated in the container And a second portion having a vent formed therein.

  In the above battery, the first portion may be located outside the outer edge of the peripheral joint.

  In the above battery, the outer shape of the first portion may protrude from the outer shape of the second portion in the thickness direction of the battery when viewed along the extending direction of the air passage.

  In the above battery, the first portion may have a larger cross-sectional area in a cross section orthogonal to the extending direction of the air passage than the second portion.

  In the above battery, the laminate has at least a base material layer, a barrier layer, and a thermally fusible resin layer in this order, and the thermally fusible resin layers face each other between the first accommodation portion and the second accommodation portion. It may be arranged to

  According to the battery of the present invention, since the valve device is attached to the peripheral joint portion of the container, accurate control of the pressure for degassing is possible. Also, the housing has a bulging portion that bulges from the peripheral joint, and the inner end of the valve device is located outside the outer edge of the bulging portion of the housing. That is, the valve device does not reach the inside of the bulging portion. Therefore, the valve device can be prevented from damaging the battery element in the bulging portion.

FIG. 1 is a plan view of a battery according to Embodiment 1. It is II-II sectional drawing of FIG. It is a figure showing a container. It is IV-IV sectional drawing of FIG. It is IV-IV sectional drawing of FIG. 1 in another example. It is a figure which shows an example of the cross-section of a packaging material. FIG. 1 is a plan view of a valve device according to Embodiment 1. It is VI-VI sectional drawing of FIG. It is VII-VII sectional drawing of FIG. It is a VIII-VIII sectional view of Drawing 1, and is a figure for explaining the attachment state of a valve device. FIG. 2 is a partially enlarged view of a circle indicated by a broken line in FIG. The elements on larger scale in the circle | round | yen shown with the broken line of FIG. 1 in another example. It is a flowchart which shows the manufacture procedure of a battery. It is a figure which shows the operation | movement which mounts a valve apparatus between a flange part and packaging material. FIG. 10 is a plan view of a valve device according to Embodiment 2. It is XII-XII sectional drawing of FIG. FIG. 14 is a plan view of a valve device according to Embodiment 3. It is XIV-XIV sectional drawing of FIG. FIG. 20 is a plan view of the valve device in Embodiment 4; It is XVI-XVI sectional drawing of FIG. FIG. 20 is a plan view of a valve device according to Embodiment 5. FIG. 21 is a plan view of a valve device according to Embodiment 6. It is XIX-XIX sectional drawing of FIG. FIG. 20 is a plan view of the valve device in Embodiment 7; It is XXI-XXI sectional drawing of FIG. It is a figure which shows a mode at the time of attachment to the container of a valve apparatus. It is a figure which shows the cross section of the valve apparatus in the modification 1. FIG. It is a figure which shows the cross section of the valve apparatus in the modification 2. FIG. It is a figure which shows the cross section of the valve apparatus in the modification 3. FIG. FIG. 20 is a plan view of a valve device in a fourth modification. It is XXVII-XXVII sectional drawing of FIG. It is a top view of the packaging material in the modification 5. FIG. It is XXIX-XXIX sectional drawing of FIG.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In the drawings, the same or corresponding portions are denoted by the same reference characters and description thereof will not be repeated.

[1. Embodiment 1]
<1-1. Battery Overview>
FIG. 1 is a plan view of a battery 10 according to the first embodiment. FIG. 2 is a cross-sectional view taken along line II-II of FIG. The battery 10 has a configuration in which the positive electrode and the negative electrode of the tab 300 are disposed on the opposite side, and for example, in consideration of electric vehicles such as electric vehicles and hybrid vehicles using many batteries connected in series to use at high voltage.

  As shown in FIGS. 1 and 2, the battery 10 includes a container 100, a battery element 400, a tab 300, a tab film 310, and a valve device 200.

  The container 100 includes the packaging materials 110 and 120. At the peripheral portion of the container 100, the packaging materials 110 and 120 are heat-sealed to form a peripheral joint portion 130. That is, at the peripheral bonding portion 130, the packaging materials 110 and 120 are fused to each other. The peripheral edge joint portion 130 according to the first embodiment is formed by heat sealing, but is not limited thereto. For example, the peripheral edge joint portion 130 can also be formed by ultrasonic sealing. In any case, the peripheral joint 130 means a portion where the packaging materials 110 and 120 are fused and integrated. The packaging materials 110 and 120 will be described in detail later.

  Battery element 400 is, for example, a storage member such as a lithium ion battery (secondary battery) or a capacitor. The battery element 400 is accommodated in the internal space S1 of the container 100. When an abnormality occurs in the battery element 400, gas may be generated in the container 100. Also, for example, when the battery element 400 is a capacitor, gas may be generated in the container 100 due to a chemical reaction in the capacitor.

  The tab 300 is a metal terminal used for input and output of power in the battery element 400. One end of the tab 300 is electrically connected to the electrode (positive electrode or negative electrode) of the battery element 400, and the other end protrudes outward from the edge of the container 100.

  The metal material which comprises the tab 300 is aluminum, nickel, copper etc., for example. For example, when battery element 400 is a lithium ion battery, tab 300 connected to the positive electrode is usually composed of aluminum or the like, and tab 300 connected to the negative electrode is usually composed of copper, nickel or the like.

  In the battery 10, two tabs 300 are included. One of the tabs 300 is sandwiched between the packaging materials 110 and 120 via the tab film 310 at an end portion in the arrow L direction of the peripheral bonding portion 130 of the container 100. The other tab 300 is sandwiched between the packaging materials 110 and 120 via the tab film 310 at the end of the peripheral bonding portion 130 of the container 100 in the direction of the arrow R.

  The tab film 310 is an adhesive protective film and is configured to adhere to both the packaging materials 110 and 120 and the tab 300 (metal). By means of the tab film 310, the metal tab 300 can be fixed with the packaging material 110, 120. Further, when the tab film 310 is used particularly at high voltage, it preferably includes an insulating layer, a heat-resistant layer or a heat-resistant component and has a short circuit preventing function.

  The valve device 200 switches between the open state and the closed state according to the pressure in the container 100. The valve device 200 is a member that brings the internal space S1 of the container 100 into communication with the external space in the open state. The valve device 200 is configured to discharge the gas in the container 100 to the outside when the pressure in the container 100 exceeds a predetermined value due to the gas generated in the container 100. . On the other hand, in the closed state, the valve device 200 seals the internal space S1 of the container 100 from the external space.

  The housing of the valve device 200 is preferably made of a material that directly adheres to the innermost layer of the packaging material 110, 120, and a resin having the same heat sealing property as the innermost layer of the packaging material 110, 120, for example, polypropylene (PP) Etc. It is preferable to be comprised by resin, such as. If a different material other than PP is used for reasons such as heat resistance etc., it is effective to seal by interposing a film that can be adhered to both the different material and PP, like the tab film used for the tab. . The valve device 200 is sandwiched between the packaging materials 110 and 120 at the end portion side in the arrow F direction of the peripheral bonding portion 130 of the container 100. The valve device 200 will be described in detail later.

  In the battery 10 according to the first embodiment, various structural devices are adopted in attaching the valve device 200 to the housing 100. Hereinafter, the configuration of the container 100, the configuration of the valve device 200, the attachment state of the valve device 200 to the container 100, and the method of manufacturing the battery 10 will be described in order.

  In addition, the direction which each of arrow LUDFUB shows is common in each drawing. Hereinafter, the arrow LR direction is also referred to as "the width direction of the battery 10", and the arrow UD direction is also referred to as "the thickness direction of the battery 10." The arrow LR direction, the arrow UD direction, and the arrow FB direction are orthogonal to each other. In addition, the direction of the arrow UD may be referred to as “vertical direction”. At this time, the U side is the upper side and the D side is the lower side, with reference to FIG. 3 described later.

<1-2. Configuration of Containment>
FIG. 3 is a view showing the container 100. As shown in FIG. As shown in FIG. 3, the container 100 has an internal space S1 in which the battery element 400 is accommodated and covers the internal space S1 from the lower side in the thickness direction of the battery 10, and the internal space S1 is a battery A packaging material 120 covering from the upper side in the thickness direction of 10 is included. Each of the packaging materials 110 and 120 is made of a so-called laminate film, and the shape in a plan view is substantially the same rectangular shape.

  The packaging material 110 includes a formed portion 112 which is formed so as to form an internal space S1 having a substantially rectangular parallelepiped shape, and a flange portion 114 extending in the arrow FB direction and the arrow LR direction along the outer edge of the formed portion 112. It contains. That is, the flange portion 114 surrounds the molding portion 112. The flange portion 114 extends substantially in the same plane, and the formed portion 112 bulges in the direction of arrow D shown in FIG. 3 from the flange portion 114 toward the lower side in the thickness direction of the battery 10. In the forming portion 112, the surface in the direction of the arrow U is open. The battery element 400 (FIG. 1) is disposed in the internal space S1 through the open surface. That is, the packaging material 110 is a tray-type laminate case having a space (substantially the same as the internal space S1) inside the molding portion 112. The packaging material 110 covers the internal space S <b> 1 from the lower side in the thickness direction of the battery 10.

  On the other hand, the packaging material 120 is a sheet that is a lid that covers the internal space S1 mainly defined by the molding portion 112 from the upper side in the thickness direction of the battery 10. The peripheral part of the packaging material 120 which is a lid is stacked on the flange part 114 which is the peripheral part of the tray-type packaging material 110, and both peripheral parts are fused. The peripheral junction 130 formed in this manner extends over the entire outer periphery of the housing 100 and is formed in a square ring shape.

  4A is a cross-sectional view taken along line IV-IV of FIG. As shown in the figure, the formed portion 112 is disposed inside the inner edge P2 of the peripheral joint portion 130, and rises from the inner edge P3 of the flange portion 114. Therefore, the molding portion 112 bulges in the arrow D direction more than the peripheral edge joint portion 130. In this example, the inner edge P2 of the peripheral joint 130 and the inner edge P3 of the flange portion 114 (in other words, the outer edge of the formed portion 112) coincide with each other. In the figure, the hatched area is a portion welded at the peripheral edge joint portion 130. FIG. 4B is a cross-sectional view taken along line IV-IV of FIG. 1 in another example. As in the example of FIG. 4B, the inner edge P2 of the peripheral joint 130 may be located outside the inner edge P3 of the flange portion 114 (in other words, the outer edge of the formed portion 112).

  FIG. 5 is a view showing an example of the cross-sectional structure of the packaging materials 110 and 120. As shown in FIG. As shown in FIG. 5, each of the packaging materials 110 and 120 is a laminate in which a base material layer 31, an adhesive layer 32, a barrier layer 33, an adhesive layer 34 and a heat fusible resin layer 35 are laminated in this order. It is. Although each of the packaging materials 110 and 120 does not necessarily have to include the layers shown in FIG. 5, typically, at least the base material layer 31, the barrier layer 33 and the heat fusible resin layer 35 Have in order. The packaging materials 110 and 120 are arranged such that the respective heat fusible resin layers 35 face each other.

  In the container 100, the base material layer 31 is the outermost layer, and the thermally fusible resin layer 35 is the innermost layer. With the battery element 400 (FIG. 2) disposed in the internal space S1 (FIG. 3) at the time of assembly of the battery 10, the heat fusible resin layers 35 located on the periphery of each of the packaging materials 110 and 120 By heat sealing, the peripheral joint 130 is formed. At this time, the battery element 400 is sealed in the container 100, the valve device 200 is fused and fixed to the peripheral bonding portion 130, and the tab 300 is also fused to the peripheral bonding portion 130 via the tab film 310. It is fixed. Hereinafter, each layer contained in the packaging materials 110 and 120 will be described. The thickness of the packaging materials 110 and 120 is, for example, about 50 to 200 μm, preferably about 90 to 160 μm.

(1-2-1. Base layer)
The base material layer 31 is a layer which functions as a base material of the packaging materials 110 and 120, and is a layer which forms the outermost layer side of the container 100.

  The material for forming the base material layer 31 is not particularly limited, but typically has insulating properties, and, for example, polyester, polyamide, epoxy, acrylic, fluorocarbon resin, polyurethane, silicone resin, phenol, polyetherimide, Polyimides, polycarbonates, and mixtures and copolymers thereof may be mentioned. The base material layer 31 may be, for example, a resin film formed of the above-described resin, or may be formed by applying the above-described resin. The resin film may be an unstretched film or a stretched film. As a stretched film, a uniaxially stretched film and a biaxially stretched film are mentioned, and a biaxially stretched film is preferable. As a stretching method for forming a biaxially stretched film, for example, a sequential biaxial stretching method, an inflation method, a simultaneous biaxial stretching method and the like can be mentioned. Furthermore, the base material layer 31 may be a single layer or may be composed of two or more layers. When the base material layer 31 is constituted by two or more layers, the base material layer 31 may be a laminate obtained by laminating resin films with an adhesive or the like, or co-extrusion of resin to form two or more layers. It may be a laminated body of resin films. In addition, a laminate of resin films in which the resin is co-extruded into two or more layers may be used as the base material layer 31 without being stretched, or may be used as the base material layer 31 by uniaxial stretching or biaxial stretching. As a specific example of a laminate of resin films of two or more layers, the substrate layer 31 is a laminate of a polyester film and a nylon film, a laminate of two or more layers of nylon films, a laminate of two or more layers of polyester films And the like, and preferably, a laminate of a stretched nylon film and a stretched polyester film, a laminate of two or more stretched nylon films, and a laminate of two or more stretched polyester films. For example, when the base material layer 31 is a laminate of two resin films, a laminate of a polyester resin film and a polyester resin film, a laminate of a polyamide resin film and a polyamide resin film, or a polyester resin film and a polyamide resin film A laminate is preferred, and a laminate of polyethylene terephthalate film and polyethylene terephthalate film, a laminate of nylon film and nylon film, or a laminate of polyethylene terephthalate film and nylon film is more preferred. Moreover, it is preferable that a polyester resin is located in the outermost layer of the base material layer 31.

  The thickness of the base layer 31 is, for example, about 3 to 50 μm, preferably about 10 to 35 μm.

(1-2-2. Adhesive layer)
The adhesive layer 32 is a layer disposed on the base layer 31 as necessary in order to impart adhesion to the base layer 31. That is, the adhesive layer 32 is provided between the base layer 31 and the barrier layer 33 as needed.

  The adhesive layer 32 is formed of an adhesive that can bond the base layer 31 and the barrier layer 33. The adhesive used to form the adhesive layer 32 may be a two-part curable adhesive or a one-part curable adhesive. The adhesion mechanism of the adhesive used to form the adhesive layer 32 is not particularly limited, and may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, a thermocompression bonding type, and the like.

  The thickness of the adhesive layer 32 is, for example, about 1 to 10 μm, preferably about 2 to 5 μm.

(1-2-3. Barrier layer)
The barrier layer 33 is a layer having a function of preventing the penetration of water vapor, oxygen, light and the like into the battery 10, in addition to the strength improvement of the packaging materials 110 and 120. As a raw material which comprises the barrier layer 33, metals, such as aluminum, stainless steel, and titanium, are mentioned, for example, Preferably aluminum is mentioned. The barrier layer 33 can be formed of, for example, a metal foil, a metal vapor deposition film, an inorganic oxide vapor deposition film, a carbon-containing inorganic oxide vapor deposition film, a film provided with these vapor deposition films, or the like. It is preferable to form, and it is more preferable to form with aluminum foil. From the viewpoint of preventing the occurrence of wrinkles and pinholes in the barrier layer 33 during the production of each packaging material, the barrier layer is made of, for example, annealed aluminum (JIS H4160: 1994 A8021 H-O, JIS H 4160: 1994 It is more preferable to form by soft aluminum foil, such as A8079H-O, JISH4000: 2014 A8021P-O, JISH4000: 2014 A8079P-O).

  The thickness of the barrier layer 33 is not particularly limited as long as it functions as a barrier layer such as water vapor, but can be, for example, about 10 to 100 μm, preferably about 20 to 80 μm.

(1-2-4. Adhesive layer)
The adhesive layer 34 is a layer provided as needed between the barrier layer 33 and the heat-fusible resin layer 35 in order to firmly bond the heat-fusible resin layer 35.

  The adhesive layer 34 is formed of an adhesive capable of adhering the barrier layer 33 and the heat fusible resin layer 35. The composition of the adhesive used to form the adhesive layer 34 is not particularly limited, and is, for example, a resin composition containing an acid-modified polyolefin. The acid-modified polyolefin is not particularly limited as long as it is an acid-modified polyolefin, but preferably includes polyolefins graft-modified with an unsaturated carboxylic acid or an anhydride thereof.

  The thickness of the adhesive layer 34 is, for example, about 1 to 50 μm, preferably about 2 to 40 μm.

(1-2-5. Heat fusible resin layer)
The heat fusible resin layer 35 forms the innermost layer of the container 100. The heat fusible resin layer 35 seals the battery element 400 inside the containing body 100 by heat-fusing the heat fusible resin layer facing each other at the periphery of the containing body 100. In addition, by covering the barrier layer with the heat fusible resin with a certain thickness or more, the insulation between the electrolytic solution and the barrier layer metal can be maintained.

  The resin component used for the heat fusible resin layer 35 is not particularly limited as long as heat fusible is possible, and examples thereof include polyolefin and acid-modified polyolefin.

  Examples of polyolefins include polyethylenes such as low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, etc .; homopolypropylene, block copolymers of polypropylene (for example, block copolymers of propylene and ethylene), random copolymers of polypropylene ( For example, crystalline or amorphous polypropylene such as a random copolymer of propylene and ethylene); terpolymer of ethylene-butene-propylene and the like can be mentioned. Among these polyolefins, preferably polyethylene and polypropylene are mentioned. The acid-modified polyolefin is not particularly limited as long as it is an acid-modified polyolefin, and preferably includes polyolefins graft-modified with an unsaturated carboxylic acid or an anhydride thereof.

  The thickness of the heat-fusible resin layer 35 is not particularly limited, but is preferably 100 μm or less, more preferably about 15 to 90 μm, and still more preferably about 30 to 80 μm.

<1-3. Configuration of valve device>
FIG. 6 is a plan view of the valve device 200. FIG. The valve device 200 is a degassing valve for adjusting the pressure in the container 100, and is a return valve capable of repeatedly degassing. As shown in FIG. 6, the valve device 200 includes a valve function portion 210 and a seal attachment portion 220. Although the details will be described later, at least a portion of the seal attaching portion 220 is fixed by being sandwiched between the packaging materials 110 and 120 (FIG. 2). By heat sealing the seal attachment portion 220, the outer peripheral surface of the seal attachment portion 220 and the thermally fusible resin layer 35, which is the innermost layer of the packaging materials 110 and 120, are fused and joined. It becomes a state.

  The valve function portion 210 and the seal attachment portion 220 are aligned in the arrow FB direction, and the seal attachment portion 220 is disposed more in the arrow B direction. The seal attachment portion 220 is connected to the end (inner end) of the valve function portion 210 in the arrow B direction. The outer shapes of the valve function portion 210 and the seal attachment portion 220 are each substantially cylindrical with a central axis parallel to the direction of the arrow FB, and are coaxial with each other. Here, the central axis common to both is represented by reference numeral C1.

  In the seal attachment portion 220, an R is formed at the corner of the end in the arrow B direction. That is, in the seal attachment portion 220, R (for example, R = 0.2 mm to 2.0 mm) is formed at the corner in plan view of the end opposite to the valve function portion 210 side. In the specification of the present application, the rounded corner is expressed as "R is formed". Here, “R is formed” is structurally the same as chamfering, and means that the corners are rounded, and further, “R” alone is Used to mean the radius of corner roundness. Although it is possible to chamfer the sharp corners generated in the manufacturing process of the valve device 200 and round the corners (form R), the housing of the valve device 200 is a resin molded article In such a case, it is also possible to form R without chamfering such as cutting by shaping so as to have rounded corners from the beginning.

  7 is a cross-sectional view taken along the line VI-VI of FIG. As shown in FIG. 7, in the valve device 200, the outer shape of a cross section (hereinafter sometimes referred to as “FB cross section”) orthogonal to the arrow FB direction of each of the valve function portion 210 and the seal attachment portion 220 is a perfect circle It is. The seal attachment portion 220 as a whole has a substantially cylindrical shape, and an air passage A1 is formed inside the seal attachment portion 220. The air passage A1 extends along the arrow FB direction. The cross section of the air passage A1 is in the shape of a perfect circle, the center of which is on the central axis C1. The radial thickness of the seal attachment portion 220 with respect to the central axis C1 is substantially constant along the circumferential direction with respect to the central axis C1.

  In the valve device 200, the length L2 of the valve function portion 210 in the thickness direction (direction of arrow UD) of the battery 10 is longer than the length L1 of the seal attachment portion 220 in the thickness direction of the battery 10. The length L2 of the valve function portion 210 in the width direction (arrow LR direction) of the battery 10 is longer than the length L1 of the seal attachment portion 220 in the width direction of the battery 10. That is, the diameter of the FB cross section of the valve function portion 210 is longer than the diameter of the FB cross section of the seal mounting portion 220, and the cross sectional area of the valve functional portion 210 in the FB cross section is larger than the cross sectional area of the seal mounting portion 220 in the FB cross section. . Further, when the valve device 200 is viewed in the arrow F direction, the outer shape of the seal attachment portion 220 is included in the outer shape of the valve function portion 210. In other words, when the valve device 200 is viewed in the arrow F direction, the valve function portion 210 protrudes from the outer shape of the seal attachment portion 220 in each direction including the thickness direction of the battery 10 (arrow UD direction). As a result, a step is formed at the boundary between the valve function portion 210 and the seal attachment portion 220 (FIG. 6). Due to this step, the valve device 200 has a shape in which the diameter of the valve attachment portion 220 is discontinuously increased from the seal attachment portion 220.

  8 is a cross-sectional view taken along the line VII-VII in FIG. As shown in FIG. 8, R (for example, R = 0.2 mm to 2.0 mm) is formed at the end of the seal attachment portion 220 in the direction of the arrow B. In addition, an air passage A1 is formed inside the seal attachment portion 220. The air passage A1 guides, for example, the gas generated in the housing 100 to the valve function unit 210.

  Inside the valve function unit 210, a valve mechanism configured to discharge the gas generated in the container 100 (FIG. 1) to the outside of the container 100 is provided. Specifically, the valve function unit 210 includes a cylindrical body 211, an O-ring 212, a ball 214, a spring 216, and a membrane 218. That is, the valve function unit 210 is provided with a ball spring type valve mechanism. In the first embodiment, the valve device 200 is a return valve that requires a complex valve mechanism capable of repeated degassing, but a simpler valve mechanism capable of one-time degassing is sufficient. It is good also as a destructive valve. The valve mechanism provided in the valve function portion 210 is not particularly limited as long as the pressure in the container 100 which is increased due to the gas can be reduced repeatedly only once or a plurality of times, for example, poppet type, duck bill It may be a valve mechanism such as a mold, an umbrella type or a diaphragm type.

  The cylindrical body 211 extends along the central axis C1 and defines a space S2 penetrating in the direction of the arrow FB. The space S2 communicates with the air passage A1 in the seal mounting portion 220, and the O-ring 212, the ball 214, the spring 216 and the membrane 218 are disposed in the space S2. In the space S2, the O-ring 212, the ball 214, the spring 216 and the membrane 218 are disposed in this order in the direction of the arrow F.

The cylindrical body 211 has a valve seat 211a facing the space S2. The valve seat 211a defines an inverted conical space expanding in the direction of arrow F in the space S2. The valve seat 211a receives the ball 214 as a valve body biased by the spring 216, and at this time, a closed state of the valve function portion 210 is formed. When the O-ring 212 is seated on the valve seat 211a, the O-ring 212 eliminates the gap between the ball 214 and the valve seat 211a, and helps to enhance the sealing performance in the closed state. The O-ring 212 is a hollow circular ring and is made of, for example, fluorine rubber. Each of the ball 214 and the spring 216 is made of, for example, stainless steel. The ball 214 may be made of resin. Membrane 218, for example, ^10-2 have to 10 ⁰ [mu] m approximately pore diameter (pore For diameter), without leaking the electrolyte is composed of a PTFE membrane as the only gas permeable (permselective). In addition, PTFE is the meaning of polytetrafluoroethylene (polytetrafluoroethylene). In addition, since the PTFE membrane is a soft material, it can be used that is integrally molded and reinforced with a mesh or non-woven fabric such as polypropylene or polyester when the strength is insufficient.

  With the valve device 200 attached to the container 100, when the pressure in the container 100 reaches a predetermined pressure, the gas guided from the air passage A1 pushes the ball 214 in the direction of the arrow F. When the ball 214 is pressed and separated from the valve seat 211a, the spring 216 is contracted to form an open state of the valve function portion 210. In this open state, the gas in the container 100 passes through the gap formed between the ball 214 and the O-ring 212, passes through the membrane 218, and is exhausted from the exhaust port O1 to the outside of the container 100. . When the gas is exhausted and the force pressing the ball 214 in the direction of the arrow F weakens, the spring 216 expands and the force biasing the ball 214 in the direction of the arrow B becomes larger than this. As a result, the closed state of the valve function unit 210 is formed again.

<1-4. Mounting condition of valve device>
FIG. 9 is a cross-sectional view taken along the line VIII-VIII of FIG. 1 and is a view for explaining the mounting state of the valve device 200. As shown in FIG. FIG. 10A is a partially enlarged view in a circle shown by a broken line in FIG. As shown in these figures, the valve function portion 210 of the valve device 200 is located outside the outer edge P1 of the peripheral joint 130. On the other hand, a part of the seal attachment portion 220 of the valve device 200 is sandwiched between the heat fusible resin layer 35 of the packaging material 110 and the heat fusible resin layer 35 of the packaging material 120 at the peripheral bonding portion 130. There is. Then, the outer peripheral surface of the seal attachment portion 220 and the thermally fusible resin layer 35 which is the innermost layer of the packaging materials 110 and 120 are in a state of being mutually fused and joined. In FIG. 9, for the sake of convenience, the heat fusible resin layer is used to describe that the valve device 200 is in a state of being fused and joined to the heat fusible resin layer 35 of the packaging material 110, 120. The heat-sealable resin layer 35 is provided on the entire surface of the packaging materials 110 and 120, although FIG.

  In battery 10 according to the first embodiment, seal attaching portion 220 is sandwiched between heat fusible resin layer 35 at peripheral junction 130 and valve function portion 210 is sandwiched between heat fusible resin layer 35 at peripheral junction 130. The reasons for failure are described below.

  Temporarily, it is assumed that the valve function part 210 is pinched | interposed into the heat-fusible resin layer 35 in the peripheral junction part 130. In this case, when the heat fusible resin layers 35 are fused to each other at the periphery of the packaging materials 110 and 120 (at the time of heat sealing), the applied heat and pressure cause the valve mechanism in the valve function unit 210 to break down. there's a possibility that.

  In the battery 10 according to the first embodiment, the seal attachment portion 220 is sandwiched between the heat fusible resin layer 35 at the peripheral bonding portion 130, and the valve function portion 210 is interposed between the heat fusible resin layer 35. It is not done. Therefore, in the battery 10, a large pressure and heat are not applied to the valve function part 210 at the time of heat sealing. That is, in the battery 10, failure of the valve mechanism due to the pressure and heat applied at the time of heat sealing is suppressed by not sandwiching the valve function part 210 by the heat-fusible resin layer 35.

  Further, in the battery 10 according to the first embodiment, as described above, the diameter of the cross section of the seal attachment portion 220 is shorter than the diameter of the cross section of the valve function portion 210. Therefore, as compared with the case where the diameter of the cross section of the seal attachment portion 220 is equal to or larger than the diameter of the cross section of the valve function portion 210, in the thickness direction of the battery in the portion where the seal attachment portion 220 is pinched The difference between the length L4 and the length L3 in the thickness direction of the battery in the portion of the peripheral edge joint portion 130 where the seal attachment portion 220 is not sandwiched is small. As the difference is larger, the outer peripheral surface of the seal attaching portion 220 is fused with the heat fusible resin layer 35, which is the innermost layer of the packaging material 110, 120, to be in a state of being joined without gaps. It is necessary to increase the pressure of the seal. As a result, the pressure applied to the periphery of the container 100 for heat sealing increases. When the pressure is increased, the heat-fusible resin layer 35 may be thinned particularly at the position where the seal attachment portion 220 is held, and further at the position where the tab film 310 and the tab 300 are held. When the heat fusible resin layer 35 becomes thin, dielectric breakdown may occur in the battery 10.

  In the battery 10 according to the first embodiment, as described above, the difference between the length L4 and the length L3 is small. Therefore, when the peripheral edge of the container 100 is pinched by the heat sealing machine, pressure and heat are appropriately applied to the heat-fusible resin layer over the entire peripheral edge of the container 100. As a result, according to the battery 10, while the possibility of occurrence of dielectric breakdown in the battery 10 is reduced, the opposing heat fusible resin layer 35 is appropriately fused to make the seal attachment portion 220 firmly in the container 100. It can be fixed.

  Further, in battery 10 according to the first embodiment, as shown in FIG. 10A, peripheral edge joint portion 130 has a concave portion recessed outward in the vicinity of seal attaching portion 220. More specifically, the inner edge P2 of the peripheral joint 130 includes three lines K1 to K3 adjacent to each other along the extending direction of the inner edge P2 in the vicinity of the seal attachment portion 220. Among these, the first line K1 extends to intersect the seal mounting portion 220. The second line K2 is continuous with one end of the first line K1, and the third line K3 is continuous with the other end of the first line K1. The second line K2 and the third line K3 extend at the same position in the arrow FB direction. The first line K1 obliquely extends outward from the end of the second line K2, then extends in the direction of the arrow R, and then extends inward to the end of the third line K2. Thus, the first line K1 is located outside the second line K2 and the third line K2, and extends between the second line K2 and the third line so as to run outside the lines K2 and K3. ing. As a result, the internal space S1 has a space S3 projecting outward toward the seal attachment portion 220 in the vicinity of the seal attachment portion 220 from the space in the molding portion 112 in which the battery element 400 is disposed.

  In the battery 10 according to the first embodiment, the inner end 221 of the seal mounting portion 220 is located outside the outer edge P3 of the formed portion 112 (which coincides with the inner edge of the flange portion 114). Therefore, the possibility that the inner end portion of the seal attachment portion 220 comes in contact with the battery element 400 disposed in the molding portion 112 is reduced, and damage to the battery element 400 can be suppressed.

  Further, in the battery 10 according to the first embodiment, the inner end 221 of the seal attachment portion 220 reaches the inner end edge P2 of the peripheral joint portion 130 and further protrudes toward the inner space S1 from there. However, the inner end 221 of the seal attachment portion 220 is located in the above space S 3 and does not reach the inside of the formed portion 112. On the other hand, if the inner end 221 of the seal attachment portion 220 is flush with the inner edge P2 of the peripheral joint 130 or outside the inner edge P2, various problems occur in the function of the valve device 200. It can occur. For example, due to the seal heat and pressure applied to the seal attachment 220 when forming the peripheral joint 130, the inner end of the seal attachment 220 may be deformed. In addition, a part of the melted packaging material 110 and 120 may enter into the air passage A1 of the seal attachment portion 220 from the inner end 221 side, and the air passage A1 may be clogged. If the above problems occur, the valve device 200 will not function properly and will fail. However, in the first embodiment, the inner end 221 of the seal mounting portion 220 exists inside the inner edge P2 of the peripheral joint portion 130. Therefore, the inner end portion of the seal attaching portion 220 is protected at the time of formation of the peripheral edge joint portion 130, the same portion is not damaged, and the failure of the valve device 200 is suppressed.

  However, even if the inner end 221 of the seal mounting portion 220 is located outside the outer edge P3 of the molded portion 112, the end of the seal mounting portion 220 in the direction of arrow B depending on the usage of the battery 10. The part (inner end) may come in contact with the battery element 400. In the battery 10 according to the first embodiment, as described above, R is formed at the inner end of the seal attachment portion 220 (FIG. 6). Therefore, even if the inner end of the seal attachment portion 220 contacts the battery element 400, the possibility of the inner end damaging the battery element 400 is low. Further, depending on the use condition of the battery 10, the inner end of the seal attachment portion 220 may come in contact with the heat-fusible resin layer 35 of the packaging material 120. In the battery 10 according to the first embodiment, as described above, since R is formed at the inner end of the seal attachment portion 220, the inner end portion of the seal attachment portion 220 temporarily melts the packaging material 120. Even if it contacts the conductive resin layer 35, the possibility of the inner end portion damaging the heat-fusible resin layer 35 is low.

  In the example of FIG. 10A, the end (inner end) in the direction of arrow B of the valve function portion 210 is not in contact with the outer end edge P1 of the peripheral joint 130, and is spaced outward from the outer end edge P1. There is. However, as in the example of FIG. 10B, the valve device 200 can also be mounted such that the inner end of the valve function portion 210 contacts the outer edge P1 of the peripheral joint 130. In this case, by utilizing the step between the valve function portion 210 and the seal attachment portion 220, the valve device 200 can be reliably positioned relative to the peripheral joint portion 130. Therefore, the inner end of the seal attaching portion 220 is designed by designing the length of the seal attaching portion 220 in the arrow FB direction and the seal width of the peripheral joint 130 in the arrow FB direction so that the former is longer than the latter. 221 can be reliably projected from the inner edge P2 of the peripheral joint 130 in the space S3.

<1-5. Manufacturing method>
FIG. 11 is a flowchart showing the manufacturing procedure of the battery 10. For example, the battery 10 is manufactured by a manufacturing apparatus.

  Referring to FIG. 11, the manufacturing apparatus places each part in housing 100 (step S100). For example, the manufacturing apparatus places the battery element 400 to which the tab 300 with the tab film 310 is electrically connected by welding, on the flange portion 114 of the packaging material 110 by placing the battery element 400 in the internal space S1 in the packaging material 110. Then, the tab 300 with the tab film 310 is placed, and then, the valve device 200 is placed on the flange portion 114 of the packaging material 110. The battery element 400 is placed in the internal space S1 of the packaging material 110, and then the tab 300 with the tab film 310 is welded to the battery element 400 for electrical connection and the flange portion 114 of the packaging material 110. It is also possible to place the valve 300 with the tab film 310 with the tab film 310 mounted thereon and then the flange portion 114 of the packaging material 110. Then, the manufacturing apparatus places the packaging material 120 on the packaging material 110.

  FIG. 12 is a view showing an operation of placing the valve device 200 between the flange portion 114 of the packaging material 110 and the packaging material 120. As shown in FIG. As shown in FIG. 12, a step is formed between the valve function portion 210 and the seal attachment portion 220. Therefore, when the seal attachment portion 220 is sandwiched by the packaging materials 110 and 120, even if the valve device 200 is pushed too much toward the housing 100, the step portion is caught on the end of the packaging materials 110 and 120. Therefore, according to the battery 10, in the manufacturing process of the battery 10, the valve function part 210 can be prevented from being accidentally pinched by the packaging materials 110 and 120 (heat-fusible resin layer 35). That is, in the stepped portion, the structure of the valve function portion 210 which rises at least in the vertical direction from the seal attachment portion 220 functions as a stopper for preventing the valve function portion 210 from entering between the packaging materials 110 and 120.

  When the placement of each component is completed, the manufacturing apparatus heat-seals the periphery of the container 100 (step S110). That is, the manufacturing apparatus sandwiches the periphery of the container 100 and applies pressure and heat to the periphery of the container 100. Thereby, the heat-fusible resin layers 35 facing each other are fused to each other at the peripheral edge of the container 100, and the peripheral edge bonding portion 130 is formed. Then, the battery element 400 is sealed in the container 100, the valve device 200 is fused and fixed to the peripheral bonding portion 130, and the tab 300 is also fused to the peripheral bonding portion 130 via the tab film 310. It is fixed and the battery 10 is completed. In the heat sealing step, by degassing the inside of the container 100, unnecessary gas can be prevented from being contained in the inside of the container 100. Specifically, without bonding the entire circumference, leaving the periphery in the unbonded state in part, degassing from the periphery in the unbonded state, and finally, pressure and heat are applied to the periphery in the unbonded state In addition, the entire circumferential bond 130 can be completed. Furthermore, in the case of a battery that requires an electrolytic solution, without bonding the entire circumference, leaving the periphery in the unbonded state in part, injecting the electrolytic solution from the periphery in the unbonded state, It may be degassed and finally pressure and heat may be applied to the unbonded peripheral edge to complete the full peripheral peripheral junction 130.

  In addition, it is also effective to make the shape of the surface sandwiching the peripheral edge of the container 100 among the seal bars of the manufacturing apparatus into a shape along the outer shape of the seal attaching portion 220. In this case, the adhesion between the heat-fusible resin layers 35 at the position where the seal attachment portion 220 is sandwiched becomes stronger. Even in this case, in order to reduce the deformation and load of the packaging materials 110 and 120, it is effective to make the shape of the seal attaching portion 220 flat as in the second embodiment described later.

  In the attached drawings, the battery element 400 is shown smaller in size than the internal space S1 for the sake of convenience in order to facilitate understanding of the fact that the battery element 400 is accommodated in the internal space S1 of the container 100. ing. However, in the case of degassing as described above in the manufacturing process, the internal space S1 is reduced to be approximately the same size as the battery element 400, and can be filled by the battery element 400 with almost no gap in the final battery 10 state. .

<1-6. Feature>
As described above, in the battery 10 according to the first embodiment, the inner end 221 of the seal attachment portion 220 is on the outer side than the outer edge P3 of the formed portion 112 (corresponding to the inner edge of the flange portion 114). To position. Therefore, the possibility that the inner end portion of the seal attachment portion 220 comes in contact with the battery element 400 disposed in the molding portion 112 is reduced, and damage to the battery element 400 can be suppressed. Further, in the battery 10 according to the first embodiment, the valve device 200 protrudes from the inner edge P2 of the peripheral joint portion 130 of the housing 100 toward the internal space S1. That is, the inner end of the valve device 200 is spaced from the peripheral joint 130. Therefore, when forming the peripheral edge joint portion 130, the cause of failure of the valve device 200 such as heat or pressure applied to the peripheral edge joint portion 130 hardly acts on the inner end portion of the valve device 200. Therefore, the failure at the time of attachment of the valve apparatus 200 can be suppressed.

  The battery element 400 is an example of the “battery element” in the present invention. The container 100 is an example of the “container” of the present invention, the packaging material 110 is an example of the “first container portion” of the present invention, and the packaging material 120 is the “second container portion” of the present invention The inner space S1 is an example of the “inner space” in the present invention, the peripheral joint 130 is an example of the “peripheral joint” in the present invention, and the forming part 112 is the “interior space” of the present invention. It is an example of "the bulging part". The valve device 200 is an example of the "valve device" of the present invention, the valve function part 210 is an example of the "first part" of the present invention, and the seal attachment part 220 is the "second part" of the present invention The air passage A1 is an example of the “air passage” in the present invention. The base layer 31 is an example of the “base layer” of the present invention, the barrier layer 33 is an example of the “barrier layer” of the present invention, and the heat-fusible resin layer 35 is the “heat” of the present invention. It is an example of "a fusion bondable resin layer."

[2. Second Embodiment]
The second embodiment is different from the first embodiment in the configuration of the valve device. The other configuration is basically the same as that of the first embodiment. Here, parts different from the first embodiment will be described.

  FIG. 13 is a plan view of a valve device 200A mounted on a battery according to the second embodiment. As shown in FIG. 13, the valve device 200A includes a valve function portion 210A and a seal attachment portion 220A. The seal attachment portion 220A is a portion at least a part of which is heat sealed by being sandwiched between the packaging materials 110 and 120. The seal attachment portion 220A has a cross-sectional shape different from that of the first embodiment. The valve function portion 210A is basically the same as that of the first embodiment, but the housing and the valve mechanism are different according to the difference in the shape of the air passage A6 (FIG. 14) formed in the seal attachment portion 220A. The shape of has been partially changed.

  FIG. 14 is a cross-sectional view taken along line XII-XII of FIG. As shown in FIG. 14, in the cross section of the seal attachment portion 220A, the length L5 in the battery width direction (arrow LR direction) is longer than the length L6 in the battery thickness direction (arrow UD direction). More specifically, the cross-sectional shape of the seal attachment portion 220A is an elliptical shape.

  An air passage A6 is formed inside the seal attachment portion 220A. Also in the air passage A6, the length in the width direction of the battery is longer than the length in the thickness direction of the battery. More specifically, the cross-sectional shape of the air passage A6 is an elliptical shape.

  As described above, in the second embodiment, in the cross section of the seal attachment portion 220A, the length L5 in the width direction of the battery is longer than the length L6 in the thickness direction of the battery. That is, the length of the seal attachment portion 220A in the thickness direction of the battery is shorter than in the case where the cross-sectional shape of the seal attachment portion is a true circle (the area is the same). In this battery, the length in the thickness direction of the battery in the portion where the seal attachment portion 220A is pinched in the peripheral edge joint portion 130, and the thickness of the battery in the portion where the seal attachment portion 220A is not pinched in the peripheral edge joint portion 130. The difference with the direction length is smaller. Therefore, according to this battery, pressure and heat can be appropriately applied to the heat-fusible resin layer 35 over the entire periphery of the container 100, and the opposing heat-fusible resin layer 35 is appropriately fused. Thus, the seal attachment portion 220A of the valve device 200A can be firmly fixed to the housing 100.

  The valve device 200A is an example of the “valve device” in the present invention, the valve function part 210A is an example of the “first portion” in the present invention, and the seal attachment portion 220A is the “second part” in the present invention. "Part" is an example. The air passage A6 is an example of the "air passage" in the present invention.

[3. Embodiment 3]
The third embodiment is different from the first embodiment in the configuration of the valve device. The other configuration is basically the same as that of the first embodiment. Here, parts different from the first embodiment will be described.

  FIG. 15 is a plan view of a valve device 200B mounted on the battery according to the third embodiment. As shown in FIG. 15, the valve device 200B includes a valve function portion 210B and a seal attachment portion 220B. At least a part of the seal attachment portion 220B is a portion to be heat-sealed by being sandwiched between the packaging materials 110 and 120. The seal attachment portion 220B has a cross-sectional shape different from that of the first embodiment. The valve function portion 210B is basically the same as that of the first embodiment, but the housing and the valve mechanism are different according to the difference in the shape of the air passage A7 (FIG. 16) formed in the seal attachment portion 220B. The shape of has been partially changed.

  16 is a cross-sectional view taken along line XIV-XIV of FIG. As shown in FIG. 16, in the seal attachment portion 220B, wing-like extended end portions 40, 41 are formed at both ends in the width direction (the arrow LR direction) of the battery. Each of the wing-like extended end portions 40 and 41 has a shape which becomes thinner toward the end in the width direction of the battery. From another point of view, each of wing-like extended end portions 40 and 41 has a change in the length in the thickness direction of the battery in the direction of arrow LR as compared with the other portion (circular portion) of seal attachment portion 220. It can be said that it is a moderate part.

  In the battery according to the third embodiment, as compared with the first embodiment (in the case where the wing attachment end portions 40 and 41 are not provided in the seal attachment portion 220B), the seal attachment portion 220B of the peripheral bonding portion 130 The change in the thickness direction of the battery is smooth at the position where the seal attachment portion 220B of the peripheral edge joint portion 130 is shifted from the portion not pinched. Therefore, according to this battery, the packaging is performed at the boundary between the position where the seal attachment portion 220B is sandwiched by the heat fusible resin layer 35 and the position where the seal attachment portion 220B is not sandwiched by the heat fusible resin layer 35. Since no undue force is applied to the materials 110 and 120, the seal attachment portion 220B of the valve device 200B can be firmly fixed to the container 100.

  The valve device 200B is an example of the “valve device” in the present invention, the valve function unit 210B is an example of the “first portion” in the present invention, and the seal attachment portion 220B is the “second device” in the present invention. "Part" is an example. The wing-like extended end parts 40 and 41 are examples of the "wing-like extended end part" of this invention. The air passage A7 is an example of the "air passage" in the present invention.

[4. Embodiment 4]
The fourth embodiment differs from the first embodiment in the configuration of the valve device. The other configuration is basically the same as that of the first embodiment. Here, parts different from the first embodiment will be described.

  FIG. 17 is a plan view of a valve device 200C mounted on a battery according to the fourth embodiment. As shown in FIG. 17, the valve device 200C includes a valve function portion 210C and a seal attachment portion 220C. The seal attachment portion 220C is a portion at least a part of which is heat sealed by being sandwiched between the packaging materials 110 and 120. The seal attachment portion 220C has a cross-sectional shape different from that in the first embodiment. The valve function portion 210C is basically the same as that of the first embodiment, but the housing and the valve mechanism are different according to the difference in the shape of the air passage A2 (FIG. 18) formed in the seal attachment portion 220C. The shape of has been partially changed.

  FIG. 18 is a cross-sectional view taken along line XVI-XVI of FIG. As shown in FIG. 18, pillars 50 and 51 are formed in the seal attachment portion 220C (in the air passage A2). Each of the pillars 50 51 extends in the battery thickness direction (arrow UD direction), and both ends in the battery thickness direction are connected to the inner periphery of the seal mounting portion 220C. Further, each of the pillars 50 and 51 extends in the direction of the arrow FB in the air passage A2 (FIG. 17). The number of pillars does not necessarily have to be two, and it is sufficient if there is at least one.

  In the battery according to the fourth embodiment, since the pillars 50 and 51 are formed in the air passage A2, pressure and heat are applied to the seal attachment portion 220C sandwiched between the heat-fusible resin layers 35 facing each other. Even if, the air passage A2 is maintained. Therefore, according to this battery, it is possible to suppress breakage of the air passage A2 in the seal attachment portion 220C at the time of fusion bonding of the heat fusion bonding resin layer 35 facing each other.

  The valve device 200C is an example of the “valve device” in the present invention, the valve function unit 210C is an example of the “first portion” in the present invention, and the seal attachment portion 220C is the “second device” in the present invention. "Part" is an example. The pillars 50 and 51 are examples of the "pillar" of the present invention. The air passage A2 is an example of the "air passage" of the present invention.

[5. Fifth Embodiment]
The fifth embodiment is different from the first embodiment in the configuration of the valve device. The other configuration is basically the same as that of the first embodiment. Here, parts different from the first embodiment will be described.

  FIG. 19 is a plan view of a valve device 200D mounted on a battery according to the fifth embodiment. As shown in FIG. 19, the valve device 200D includes a valve function portion 210 and a seal mounting portion 220D. The configuration of the valve function unit 210 is the same as that of the first embodiment.

  The seal attachment portion 220D is a portion at least a part of which is heat sealed by being sandwiched between the packaging materials 110 and 120. The outer surface of the seal attachment portion 220D is different from that of the first embodiment. Specifically, the outer surface of the seal attachment portion 220D is a ground. The surface roughness Ra of the pear ground is, for example, 1 μm to 20 μm.

  In the battery according to the fifth embodiment, since the outer surface of seal mounting portion 220D is a non-abrasive, the heat fusible resin is easily melted at the position in contact with seal mounting portion 220D. Therefore, according to this battery, the seal attachment portion 220D of the valve device 200D can be firmly fixed to the housing 100 as compared with the first embodiment (when the outer surface of the seal attachment portion 220D is smooth). .

  The valve device 200D is an example of the "valve device" in the present invention, and the seal attachment portion 220D is an example of the "second portion" in the present invention.

[6. Sixth Embodiment]
The sixth embodiment differs from the first embodiment in the configuration of the valve device. The other configuration is basically the same as that of the first embodiment. Here, parts different from the first embodiment will be described.

  FIG. 20 is a plan view of a valve device 200E mounted on a battery according to the sixth embodiment. As shown in FIG. 20, the valve device 200E includes a valve function portion 210 and a seal attachment portion 220E. The configuration of the valve function unit 210 is the same as that of the first embodiment.

  The seal attachment portion 220E is a portion at least a part of which is heat sealed by being sandwiched between the packaging materials 110 and 120. The seal attachment portion 220E has an outer surface different from that of the first embodiment. Specifically, on the outer surface of the seal attachment portion 220E, a ridge portion 60 extending continuously in a circumferential direction is formed. Three ridges 60 are formed in the direction of the arrow FB in the seal attachment portion 220E. The number of the protruding portions 60 is not necessarily three, and at least one may be formed.

  FIG. 21 is a cross-sectional view taken along line XIX-XIX of FIG. As shown in FIG. 21, the cross section of the ridge portion 60 is semicircular. The semicircular R is, for example, 0.05 mm to 1.0 mm. The diameter L12 (the length in the thickness direction of the battery, the length in the width direction of the battery) in the portion where the ridge portion 60 is formed in the seal attachment portion 220E is the diameter L12 in the portion where the ridge portion 60 is not formed. It is longer than the diameter L11.

  At the time of heat sealing, the ridges 60 are in contact with the heat fusible resin layer 35 reliably, and thus are easily fused to the packaging materials 110 and 120. In the battery according to the sixth embodiment, the ridges 60 extend continuously continuously around the outer surface of the seal mounting portion 220E in the circumferential direction. Therefore, according to this battery, the heat fusible resin layer 35 and the seal attachment portion 220E can be fused in one circumferential direction of the seal attachment portion 220E. Moreover, in this battery, the contact area between the outer surface of the seal attachment portion 220E and the thermally fusible resin, as compared to the first embodiment (when the ridge portion 60 is not formed on the seal attachment portion 220E). The seal mounting portion 220E of the valve device 200E can be firmly fixed to the packaging material 110.

  The formation positions of the ridges 60 may not be present on the entire circumference or may not be continuous as long as they extend in the circumferential direction. For example, in the case of providing the wing-like extended end portions 40 and 41 as in the above-described third embodiment, it is not necessary to provide the ridge portion 60 that makes one turn including the wing-like extended ends 40 and 41. For example, it is possible not to provide the ridges 60 at the tip end portions of the wing-like extended ends 40 and 41, or not to provide the ridges 60 at the wing-like extended ends 40 and 41. Further, the ridges 60 can be formed intermittently in the circumferential direction.

  The valve device 200E is an example of the "valve device" in the present invention, and the seal attachment portion 220E is an example of the "second portion" in the present invention. The ridge portion 60 is an example of the “convex portion” in the present invention. The air passage A3 is an example of the "air passage" in the present invention.

[7. Seventh Embodiment]
The seventh embodiment differs from the first embodiment in the configuration of the valve device. The other configuration is basically the same as that of the first embodiment. Here, parts different from the first embodiment will be described.

  FIG. 22 is a plan view of a valve device 200F mounted on a battery according to the seventh embodiment. As shown in FIG. 22, the valve device 200F includes a valve function portion 210F and a seal attaching portion 220F. The seal attachment portion 220F is a portion at least a part of which is heat sealed by being sandwiched between the packaging materials 110 and 120. The valve function portion 210F and the seal attachment portion 220F have different cross-sectional shapes as compared with the first embodiment.

  FIG. 23 is a cross-sectional view taken along line XXI-XXI of FIG. As shown in FIG. 23, the cross section of the valve function part 210F is semicircular. That is, the surface in the direction of the arrow U of the valve function part 210F is flat. Further, the cross section of the seal attachment portion 220F has wing-like extended end portions 40F and 41F at both ends in the direction of the arrow LR. The surface in the arrow U direction of the seal attachment portion 220F is flat. The surface in the arrow U direction of the valve function part 210F and the surface in the arrow U direction of the seal mounting part 220F are flush with each other.

  Therefore, when the valve device 200F is disposed with the surface in the arrow U direction down, the valve device 200F does not roll. Therefore, according to the battery according to the seventh embodiment, when the valve device 200F is attached to the housing 100, the valve device 200F does not roll, so that the valve device 200F can be easily positioned.

  FIG. 24 is a view showing how the valve device 200F is attached to the container 100. As shown in FIG. As shown in FIG. 24, when attaching the valve device 200F to the housing 100, the flat surface of the valve device 200F is placed on the surface of the innermost layer of the packaging material 120. In this state, the valve device 200F does not roll. Therefore, according to the battery according to the seventh embodiment, positioning of the valve device 200F can be easily performed when the valve device 200F is attached to the housing 100. Further, in the battery state, the bulge of the peripheral joint 130 by the valve device 200F can be directed in the direction in which the container 100 is bulged, that is, upward in FIG.

  The valve device 200F is an example of the “valve device” in the present invention, the valve function part 210F is an example of the “first portion” in the present invention, and the seal attachment portion 220F is the “second part” in the present invention. "Part" is an example. The air passage A4 is an example of the "air passage" in the present invention.

[8. Modified example]
The first to seventh embodiments have been described above, but the present invention is not limited to the first to seventh embodiments, and various modifications can be made without departing from the scope of the present invention. Hereinafter, modified examples will be described. However, the following modifications can be combined as appropriate.

<8-1>
In the first to seventh embodiments, the cross section of the seal attachment portion (the seal attachment portion 220 or the like) has a shape based on a circle. However, the cross-sectional shape of the seal attachment portion is not limited to this. For example, the cross-sectional shape of the seal attachment may have a polygon based shape.

  FIG. 25 is a view showing a cross section of a valve device 200G in the first modification. As shown in FIG. 25, in the valve device 200G, the cross section of the seal mounting portion 220G has a diamond shape. In the seal attachment portion 220G, the length L7 in the width direction of the battery is longer than the length L8 in the thickness direction of the battery. In this battery, the length in the thickness direction of the battery in the portion where the seal attachment portion 220G is pinched in the peripheral edge joint portion 130, and the thickness of the battery in the portion where the seal attachment portion 220G is not pinched in the peripheral edge joint portion 130. The difference with the direction length is smaller. Therefore, according to this battery, pressure and heat can be appropriately applied to the heat-fusible resin layer 35 over the entire periphery of the container 100, and the opposing heat-fusible resin layer 35 is appropriately fused. Therefore, the seal attachment portion 220G of the valve device 200G can be firmly fixed to the housing 100.

  FIG. 26 is a view showing a cross section of a valve device 200H in the second modification. As shown in FIG. 26, in the valve device 200H, the cross section of the seal mounting portion 220H has a diamond shape or a hexagonal shape chamfered at both ends in the thickness direction of the battery. In the seal attachment portion 220H, the length L9 in the width direction of the battery is longer than the length L10 in the thickness direction of the battery. In this battery, the length in the thickness direction of the battery in the portion where the seal attachment portion 220H is pinched in the peripheral edge joint portion 130, and the thickness of the battery in the portion where the seal attachment portion 220H is not pinched in the peripheral edge joint portion 130. The difference with the direction length is smaller. Therefore, according to this battery, pressure and heat can be appropriately applied to the heat-fusible resin layer 35 over the entire periphery of the container 100, and the opposing heat-fusible resin layer 35 is appropriately fused. As a result, the seal attachment portion 220H of the valve device 200H can be firmly fixed to the container 100.

  FIG. 27 is a view showing a cross section of a valve device 200I in the third modification. As shown in FIG. 27, in the valve device 200I, the cross section of the seal attachment portion 220I has a shape in which wing-like extended end portions 40I and 41I are provided at both ends of the rhombus (in the width direction of the battery). . In this battery, as compared with, for example, the first embodiment (in the case where wing-like extending end portions 40I and 41I are not provided in seal mounting portion 220I), seal mounting portion 220I is not pinched in peripheral joint 130 The change in the thickness direction of the battery is smooth at the position where the transition is made from the portion to the portion of the peripheral edge joint portion 130 where the seal attachment portion 220I is sandwiched. Therefore, according to this battery, packaging is performed at the boundary between the position where the seal attachment portion 220I is sandwiched by the heat fusible resin layer 35 and the position where the seal attachment portion 220I is not sandwiched by the heat fusible resin layer 35. Since no undue force is applied to the materials 110 and 120, the seal attachment portion 220I of the valve device 200I can be firmly fixed to the container 100.

  FIG. 28 is a plan view of a valve device 200J according to the fourth modification. As shown in FIG. 28, the valve device 200J includes a valve function portion 210J and a seal attaching portion 220J. An air passage A5 is formed in the seal attachment portion 220J.

  29 is a cross-sectional view taken along line XXVII-XXVII of FIG. This cross section can also be said to be a plane normal to the central axis C1 of the air passage A5. As shown in FIG. 29, in the valve device 200J, the cross section of the seal mounting portion 220J has a hexagonal (polygonal) shape. Each corner of the hexagon is formed with R (e.g., R = 0.2 mm to 2.0 mm). According to this battery, for example, it is possible to reduce the possibility that the portion of seal attachment portion 220J located in housing 100 may damage battery element 400 in housing 100, and of seal attachment portion 220J. It is possible to reduce the possibility of damaging the thermally fusible resin layer 35 by the portion sandwiched between the thermally fusible resin layer 35 and reducing the insulation of the thermally fusible resin layer 35.

<8-2>
In the first to seventh embodiments, the flange portion 114 of the packaging material 110 is in a flat state. However, the shape of the flange portion 114 is not limited to this. For example, in the flange portion 114, a valve device arrangement portion for arranging the seal attachment portion 220 of the valve device 200 may be formed in advance.

  FIG. 30 is a plan view of the packaging material 110K in the fifth modification. As shown in FIG. 30, a valve device placement portion 116K is formed in the flange portion 114K.

  31 is a cross-sectional view taken along line XXIX-XXIX of FIG. As shown in FIG. 31, the valve device arrangement portion 116K formed in the flange portion 114K has a semicircular shape. The diameter of this semicircle is, for example, slightly longer than the diameter of the seal mounting portion 220. For example, with the seal attachment portion 220 disposed at the valve device placement portion 116K, heat sealing is performed on the periphery of the container. As a result, deformation of the packaging material at the time of heat sealing is suppressed, and the possibility of pinholes and breakage near the seal attachment portion 220 can be reduced. The valve device arrangement portion 116K does not necessarily have to be provided on the packaging material 110K, and may be provided on the packaging material 120. Even in this case, it is possible to obtain the same effect as in the case where the valve device placement portion 116K is provided on the packaging material 110K.

<8-3>
In the first to seventh embodiments, in the valve device (for example, the valve device 200), a step is formed at the boundary between the valve function portion (for example, the valve function portion 210) and the seal attachment portion (for example, the seal attachment portion 220). It was formed. However, the step may not necessarily be formed at the boundary between the valve function portion and the seal attachment portion. For example, the diameter of the cross section of the valve function portion may be the same as the diameter of the cross section of the seal attachment portion, and the valve function portion and the seal attachment portion may be connected in a flat manner.

<8-4>
In the first to seventh embodiments, the cross section of the air passage (for example, the air passage A1) formed in the seal attachment portion (seal attachment portion 220 or the like) has a circular base. However, the cross-sectional shape of the air passage is not limited to this. For example, the cross-sectional shape of the air passage may be a polygon based shape.

<8-5>
In the first to seventh embodiments, an R is formed at the corner of the end of the seal attachment portion (for example, the seal attachment portion 220) opposite to the valve function portion (for example, the valve function portion 210). However, R may not necessarily be formed at the corner.

<8-6>
In the first to seventh embodiments, the valve device (for example, the valve device 200) is a so-called return valve. However, the valve device does not necessarily have to be a return valve. The valve device may be, for example, a so-called rupture valve as described above or a selective permeation valve.

<8-7>
Referring again to FIG. 1, in the first to seventh embodiments, the tabs 300 are provided at both ends in the direction of the arrow LR of the housing 100, and the valve device (for example, the valve device 200) is an arrow of the housing 100. It was provided at the end in the F direction. However, the positional relationship between the valve device 200 and the tab 300 is not limited to this. For example, both tabs 300 may be arranged on the same side of the periphery of the container 100 and the valve arrangement may be arranged between two tabs 300, both tabs 300 being identical on the periphery of the container 100. The valve device may be disposed on any one side of the three sides other than the side on which the tab 300 is disposed.

<8-8>
In the first to seventh embodiments, the container 100 includes the packaging material 110 formed by embossing or the like and the packaging material 120 which is separate from the packaging material 110. However, the container 100 may not necessarily have such a configuration.

  For example, the packaging material 110 and the packaging material 120 may be integrated (connected) at one side in advance. In this case, at the end of the flange portion 114 of the packaging material 110, the packaging material 110 and the packaging material 120 are integrated (connected), and the packaging material 110 and the packaging material 120 are overlapped. The battery element 400 may be sealed in the container 100 by four-way sealing. Further, the flange portion 114 is omitted on the side where the packaging material 110 and the packaging material 120 are integrated, and the container 100 is sealed by three-way sealing in a state where the packaging material 110 and the packaging material 120 are overlapped. The battery element 400 may be sealed inside.

  Also, for example, the packaging material 120 may be formed in the same shape as the packaging material 110. Also, the container 100 may be, for example, a pouch-type container. The pouch type container may be any type such as a three-way seal type, a four-way seal type, a pillow type, and a gusset type.

<8-9>
In the first to seventh embodiments, the housing of the valve function part (for example, the valve function part 210) and the housing of the seal attachment part (for example, the seal attachment part 220) are formed of the same material (resin). The However, the housing of the valve function part and the housing of the seal attachment part do not necessarily have to be formed of the same material. For example, the housing of the valve function part and the housing of the seal attachment part may be made of different materials, and the melting point of the material of the valve function part may be higher than the melting point of the material of the seal attachment part. For example, the valve function portion is made of polypropylene (PP), and the seal attachment portion is made of a resin having a melting point higher than that of PP (for example, fluorine resin, polyester resin, polyimide resin, polycarbonate resin, acrylic resin) or metal It may be done. As resin used for a seal | sticker attachment part, the fluorine resin with a high barrier is preferable.

  In this battery, the melting point of the material of the valve function part is higher than the melting point of the material of the seal attachment part even if pressure and heat are applied to the seal attachment part at the time of fusion bonding of the heat fusion resin layer 35 facing each other. Therefore, the valve function part is unlikely to be deformed by heat. Therefore, according to this battery, it is possible to suppress the failure of the valve mechanism in the valve function part at the time of fusion bonding of the heat fusion bonding resin layer 35 facing each other.

<8-10>
In the first to seventh embodiments, the casing of the valve device 200 is made of resin, and the seal attachment portion 220 is directly sandwiched by the heat-fusible resin layer 35. However, the housing of the valve device 200 does not necessarily have to be made of resin, and may be made of, for example, metal (for example, aluminum, stainless steel). In this case, an adhesive protective film may be disposed between the seal attachment portion 220 and the heat fusible resin layer 35. The adhesive protective film is configured to adhere at least one surface to the resin, and configured to adhere at least the other surface to the metal. As the adhesive protective film, various known adhesive protective films can be adopted. For example, the same adhesive protective film as the tab film 310 can be used.

<8-11>
In the first to seventh embodiments, the outer peripheral side of the seal mounting portion (for example, the seal mounting portion 220) (the corner of the end on the opposite side to the valve functional portion (for example, the valve functional portion 210) side of the seal mounting portion) Although R was formed in R, R was not formed in the inner peripheral side of a seal attachment part (an edge of a ventilation way (for example, ventilation way A1)). However, R may be formed on the inner peripheral side of the seal attachment portion. By forming an R on the inner peripheral side of the seal mounting portion, the corner on the inner peripheral side of the seal mounting portion is scraped to reduce the possibility of dust (for example, resin, metal, etc.) falling into the container 100. be able to.

<8-12>
Referring again to FIG. 23, in the seventh embodiment, a flat surface is formed on the outer surfaces of both the valve function portion 210F and the seal attachment portion 220F. However, it is not necessary to form a plane on the outer surfaces of both the valve function portion 210F and the seal attachment portion 220F. A plane may be formed on the outer surface of at least one of the valve function portion 210F and the seal attachment portion 220F.

<8-13>
Although battery 10 of the first to seventh embodiments is a secondary battery, it may be any battery as long as it can output electricity, for example, a capacitor, an electric double layer capacitor (EDLC) Or a storage device such as a lithium ion capacitor. Furthermore, the type of secondary battery is not particularly limited, and, for example, lithium ion battery, lithium ion polymer battery, lead storage battery, nickel hydrogen storage battery, nickel cadmium storage battery, nickel iron storage battery, nickel zinc There may be mentioned a storage battery, a silver oxide / zinc storage battery, a metal air battery, a polyvalent cation battery, an all solid battery and the like.

  DESCRIPTION OF SYMBOLS 10 battery, 31 base material layer, 32 adhesive bond layer, 33 barrier layer, 34 adhesive layer, 35 heat sealable resin layer, 40, 40 I, 41, 41 I wing-like extended end part, 50, 51 pillar, 60 convex line part , 100 containers, 110, 110 K, 120 packaging materials, 112 molding parts, 114, 114 K flange parts, 116 K valve device arranging parts, 130 peripheral joint parts, 200, 200 A, 200 B, 200 C, 200 D, 200 E, 200 F, 200 G, 200H, 200I, 200J valve device, 210, 210A, 210B, 210C, 210E, 210F, 210G, 210H, 210I, valve function part, 211 housing, 212 O ring, 214 ball, 216 spring, 218 membrane, 220, 220A, 220B, 220C, 220D, 220E, 220 , 220 G, 220 H, 220 I, 220 J seal attachment portion, 221 inner end, 300 tab, 310 tab film, 400 battery element, A1, A2, A3, A4, A5 air passage, C1 central axis, O1 exhaust port, S1 internal space , S2 space, S3 space, P1 the outer edge of the peripheral joint, P2 the inner edge of the peripheral joint, P3 the inner edge of the flange, the outer edge of the molding, the K1 first line, the K2 second line, K3 third line.

Claims (12)

A battery comprising a battery element, a housing, and a valve device,
The container is formed of a laminate, has an internal space for accommodating the battery element, and covers the internal space from the first side in the thickness direction of the battery; and the internal And a second accommodating portion covering a space from the second side opposite to the first side in the thickness direction of the battery,
The valve device is attached to the container, and the internal space of the container can be communicated with an external space,
A peripheral edge joint portion is formed on the housing body by fusing the first housing portion and the second housing portion along the respective peripheral edge portions,
The valve arrangement is at least partially sandwiched between the first receiving portion and the second receiving portion at the peripheral joint,
The first housing portion is disposed inward of the inner end edge of the peripheral edge joint, and has a bulging portion which bulges toward the first side in the thickness direction of the battery than the peripheral edge joint.
The inner end of the valve arrangement is located outside the outer edge of the bulge ,
The valve device
A first portion in which a valve mechanism for discharging gas generated in the internal space of the container to the external space of the container is formed;
A second portion in which an air passage for guiding a gas generated inside the container to the valve mechanism is formed;
Including
When viewed along the direction in which the air passage extends, the outer shape of the first portion protrudes from the outer shape of the second portion in the thickness direction of the battery.
battery.   A battery comprising a battery element, a housing, and a valve device,
  The container is formed of a laminate, has an internal space for accommodating the battery element, and covers the internal space from the first side in the thickness direction of the battery; and the internal And a second accommodating portion covering a space from the second side opposite to the first side in the thickness direction of the battery,
  The valve device is attached to the container, and the internal space of the container can be communicated with an external space,
  A peripheral edge joint portion is formed on the housing body by fusing the first housing portion and the second housing portion along the respective peripheral edge portions,
  The valve arrangement is at least partially sandwiched between the first receiving portion and the second receiving portion at the peripheral joint,
  The first housing portion is disposed inward of the inner end edge of the peripheral edge joint, and has a bulging portion which bulges toward the first side in the thickness direction of the battery than the peripheral edge joint.
  The inner end of the valve arrangement is located outside the outer edge of the bulge,
  The valve device
  A first portion in which a valve mechanism for discharging gas generated in the internal space of the container to the external space of the container is formed;
  A second portion in which an air passage for guiding a gas generated inside the container to the valve mechanism is formed;
Including
  The first portion has a larger cross-sectional area in a cross section orthogonal to the extending direction of the air passage than the second portion.
battery. When viewed along the direction in which the air passage extends, the outer shape of the first portion protrudes from the outer shape of the second portion in the thickness direction of the battery.
The battery according to claim 2. The inner end of the valve arrangement extends at least to the inner edge of the peripheral joint.
The battery according to any one of claims 1 to 3 .   A battery comprising a battery element, a housing, and a valve device,
  The container is formed of a laminate, has an internal space for accommodating the battery element, and covers the internal space from the first side in the thickness direction of the battery; and the internal And a second accommodating portion covering a space from the second side opposite to the first side in the thickness direction of the battery,
  The valve device is attached to the container, and the internal space of the container can be communicated with an external space,
  A peripheral edge joint portion is formed on the housing body by fusing the first housing portion and the second housing portion along the respective peripheral edge portions,
  The valve arrangement is at least partially sandwiched between the first receiving portion and the second receiving portion at the peripheral joint,
  The first housing portion is disposed inward of the inner end edge of the peripheral edge joint, and has a bulging portion which bulges toward the first side in the thickness direction of the battery than the peripheral edge joint.
  The valve device has a valve mechanism that discharges the gas generated in the internal space of the container to the external space of the container, and a housing in which the valve mechanism is formed.
  The inner end of the valve arrangement is located outside the outer edge of the bulge and extends at least up to the inner edge of the peripheral joint, at the inner end of the housing An opening is formed in communication with the internal space of the container in the closed state of the valve mechanism.
battery. The housing is
A first portion before Kiben mechanism formed therein,
And a second portion in which an air passage for guiding a gas generated inside the container to the valve mechanism is formed.
The battery according to claim 5 . When viewed along the direction in which the air passage extends, the outer shape of the first portion protrudes from the outer shape of the second portion in the thickness direction of the battery.
The battery according to claim 6 . The first portion has a larger cross-sectional area in a cross section orthogonal to the extending direction of the air passage than the second portion.
The battery according to claim 6 or 7 . The first portion is located outside the outer edge of the peripheral joint,
A battery according to any of claims 1 to 4 and 6 to 8 . The inner end of the valve arrangement projects from the inner edge of the peripheral joint towards the inner space
The battery according to any one of claims 1 to 9 . The inner edge of the peripheral joint is located in the vicinity of the valve device, the first line intersecting the valve device, and the first line along the direction in which the inner edge of the peripheral joint extends. And second and third lines adjacent to each other on either side of the
The first line is located outside the second line and the third line,
The battery according to any one of claims 1 to 10 . The laminate has at least a base material layer, a barrier layer and a heat fusible resin layer in this order,
The heat-sealable resin layer is disposed to face each other in the first accommodation portion and the second accommodation portion.
The battery according to any one of claims 1 to 11 .