CN104040760A - 袋装电极的制造方法、袋装电极、二次电池及热熔接装置 - Google Patents

袋装电极的制造方法、袋装电极、二次电池及热熔接装置 Download PDF

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Publication number
CN104040760A
CN104040760A CN201380004991.4A CN201380004991A CN104040760A CN 104040760 A CN104040760 A CN 104040760A CN 201380004991 A CN201380004991 A CN 201380004991A CN 104040760 A CN104040760 A CN 104040760A
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China
Prior art keywords
electrode
packed
refractory layer
fomale
male
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CN201380004991.4A
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English (en)
Inventor
若井宏平
久岛和实
金泰元
中井美由纪
泽田康宏
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Nissan Motor Co Ltd
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Nissan Motor Co Ltd
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Publication of CN104040760A publication Critical patent/CN104040760A/zh
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0404—Machines for assembling batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/18—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/82—Testing the joint
    • B29C65/8207—Testing the joint by mechanical methods
    • B29C65/8215—Tensile tests
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/82—Testing the joint
    • B29C65/8207—Testing the joint by mechanical methods
    • B29C65/8223—Peel tests
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/82—Testing the joint
    • B29C65/8253—Testing the joint by the use of waves or particle radiation, e.g. visual examination, scanning electron microscopy, or X-rays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
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    • B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/11—Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
    • B29C66/112—Single lapped joints
    • B29C66/1122—Single lap to lap joints, i.e. overlap joints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/21—Particular design of joint configurations particular design of the joint lines, e.g. of the weld lines said joint lines being formed by a single dot or dash or by several dots or dashes, i.e. spot joining or spot welding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/43—Joining a relatively small portion of the surface of said articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/43—Joining a relatively small portion of the surface of said articles
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    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/72—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined
    • B29C66/723—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined being multi-layered
    • B29C66/7232—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined being multi-layered comprising a non-plastics layer
    • B29C66/72324—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined being multi-layered comprising a non-plastics layer consisting of inorganic materials not provided for in B29C66/72321 - B29C66/72322
    • B29C66/72325—Ceramics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/72—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined
    • B29C66/727—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined being porous, e.g. foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/80—General aspects of machine operations or constructions and parts thereof
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    • B29C66/812—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the composition, by the structure, by the intensive physical properties or by the optical properties of the material constituting the pressing elements, e.g. constituting the welding jaws or clamps
    • B29C66/8124—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the composition, by the structure, by the intensive physical properties or by the optical properties of the material constituting the pressing elements, e.g. constituting the welding jaws or clamps characterised by the structure of the material constituting the pressing elements, e.g. constituting the welding jaws or clamps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • B29C66/80—General aspects of machine operations or constructions and parts thereof
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    • B29C66/812—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the composition, by the structure, by the intensive physical properties or by the optical properties of the material constituting the pressing elements, e.g. constituting the welding jaws or clamps
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/81427—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the design of the pressing elements, e.g. of the welding jaws or clamps characterised by the surface geometry of the part of the pressing elements, e.g. welding jaws or clamps, coming into contact with the parts to be joined comprising a single ridge, e.g. for making a weakening line; comprising a single tooth
    • B29C66/81429—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the design of the pressing elements, e.g. of the welding jaws or clamps characterised by the surface geometry of the part of the pressing elements, e.g. welding jaws or clamps, coming into contact with the parts to be joined comprising a single ridge, e.g. for making a weakening line; comprising a single tooth comprising a single tooth
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/80—General aspects of machine operations or constructions and parts thereof
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    • B29C66/814—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the design of the pressing elements, e.g. of the welding jaws or clamps
    • B29C66/8141—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the design of the pressing elements, e.g. of the welding jaws or clamps characterised by the surface geometry of the part of the pressing elements, e.g. welding jaws or clamps, coming into contact with the parts to be joined
    • B29C66/81433—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the design of the pressing elements, e.g. of the welding jaws or clamps characterised by the surface geometry of the part of the pressing elements, e.g. welding jaws or clamps, coming into contact with the parts to be joined being toothed, i.e. comprising several teeth or pins, or being patterned
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C66/80—General aspects of machine operations or constructions and parts thereof
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    • H—ELECTRICITY
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Abstract

在袋装电极的制造方法中，将电极配置在由树脂形成的两个隔膜层之间，将耐热层配置在所述两个隔膜层中的至少一方和所述电极之间，将所述两个隔膜层、所述电极及所述耐热层进行层叠，在比所述电极更靠近外侧处，利用一对熔接片，将隔着所述耐热层而重合的所述两个隔膜层的重合部分夹持而进行加压及加热，使加压及加热后的所述重合的部分中的所述耐热层破坏，将所述两个隔膜层接合。根据上述制造方法，通过使耐热层与袋装电极一体化，从而能够减少层叠工时。

Description

袋装电极的制造方法、袋装电极、二次电池及热熔接装置
技术领域
本发明涉及袋装电极的制造方法(a method for manufacturing apacked electrode)、袋装电极、二次电池(a secondary battery)、热熔接装置(heat sealing machine)。更详细地说，本发明涉及将电极收容在袋状的隔膜内的袋装电极的制造方法、利用该制造方法而制造出的袋装电极、采用了该袋装电极的二次电池、在上述袋装电极的制造中使用的热熔接装置。
背景技术
公知有如下二次电池(下述专利文献1)，即，为了提高内部耐热性，使袋装正极(packed cathode)(收容在袋状隔膜(separatorenvelope)中的正极(cathode electrode))、耐热层、以及袋装负极(packed anode)(收容在袋状隔膜中的负极(anode electrode))依次进行层叠。
专利文献1：日本国专利3584583号公报
发明内容
在上述的二次电池中，在构成袋装正极或袋装负极的袋装隔膜时，两片隔膜被接合(熔接)，但由于耐热层也被层叠，因此需要留意，以使得不产生两片隔膜的接合(熔接)不良。
本发明的目的在于提供能够将袋装电极的隔膜可靠地接合的袋装电极的制造方法、袋装电极、二次电池、以及热熔接装置。
本发明的第1特征是提供一种袋装电极的制造方法，在该袋装电极的制造方法中，将电极配置在由树脂形成的两个隔膜层之间，将耐热层配置在所述两个隔膜层中的至少一个和所述电极之间，将所述两个隔膜层、所述电极及所述耐热层进行层叠，在与所述电极相比的外侧，利用一对熔接片，将隔着所述耐热层而重合的所述两个隔膜层的重合部分夹持而进行加压及加热，使加压及加热后的所述重合部分中的所述耐热层破坏，将所述两个隔膜层接合。
本发明的第2特征是提供一种袋装电极，该袋装电极具有：由树脂形成的两个隔膜层；电极，其配置在所述两个隔膜层之间；以及两个耐热层，它们分别配置在所述两个隔膜层和所述电极之间，在与所述电极相比的外侧，在隔着所述耐热层而重合的所述两个隔膜层的重合部分中，所述耐热层被破坏而形成将所述两个隔膜层接合的接合部。
本发明的第3特征是提供一种二次电池，该二次电池具有发电要素，该发电要素是使上述第2特征的袋装电极、和极性与所述袋装电极的极性不同的电极层叠而形成的。
本发明的第4特征是提供一种热熔接装置，该热熔接装置具有在上述第1特征的袋装电极的制造方法中所利用的至少一对熔接片，在所述至少一对熔接片中的至少一个的表面上，形成有凹凸面。
附图说明
图1是表示二次电池的实施方式的外观的斜视图。
图2是上述二次电池的分解斜视图。
图3(A)是上述二次电池的袋装正极(袋装电极)的俯视图，(B)是(A)中的ⅢB-ⅢB线剖面图。
图4是上述二次电池的负极的俯视图。
图5是上述二次电池的放大剖面图。
图6(A)是热熔接装置的实施方式的概略俯视图，(B)是上述热熔接装置的侧视图。
图7(A)是熔接片的俯视图，(B)是熔接片的侧视图，(C)是熔接片的主视图。
图8(A)是表示两片隔膜被热熔接装置的熔接头夹持的加压前状态的放大剖面图，(B)是表示加压中状态的放大剖面图。
图9(A)是表示袋装正极的熔接部的切断面的照片，(B)是(A)中的ⅠXB部的放大照片，(C)是(B)中的ⅠXC部的进一步放大的照片，(D)是(B)中的ⅠXD部的进一步放大的照片。
图10是剥离试验方法的说明图。
图11(A)是表示熔接部的表面的照片，(B)是(A)的放大照片。
图12是表示采用了金属网的熔接片的表面的照片。
图13是表示剥离试验的结果的图表。
图14是粘贴有PTFE树脂膜胶带的熔接片的放大剖面图。
图15是表示形成有球表面凹痕(dimples)的熔接片的表面的俯视图。
图16(A)是表示图12的熔接片的压痕(press pattern)的照片，(B)是表示图15的熔接片的压痕的照片，(C)是表示具有马蹄形状的凸部的熔接片的压痕的照片，(D)是表示具有长圆状的凸部的熔接片的压痕的照片。
图17(A)是表示对比例的熔接片的熔接部表面(短时间熔接)的照片，(B)是表示熔接部表面(长时间熔接)的照片。
具体实施方式
下面，参照附图说明实施方式。此外，对相同及等同的结构标注相同的标号，省略它们的重复说明。另外，附图中的各结构要素的大小、比例有时与实际的大小、比例不同。
首先，对采用了袋装电极的二次电池进行说明。然后，对用于制造该袋装电极的熔接装置、和采用了该装置的袋装电极的制造方法进行说明。
(二次电池)
如图1所示，二次电池10具有扁平矩形形状。从二次电池10的外装材料(outer cover)13的一个缘部导出有正极引线(cathode lead)11及负极引线(anode lead)12。在外装材料13的内部收容有发电要素(power-generation element)(电池要素(battery element)：层叠体(assembled laminate))15，在发电要素15中发生充放电反应。如图2所示，发电要素15由袋装正极(packed cathode)20和负极(anode)30交替地层叠而构成。袋装正极20及负极30具有片状的矩形形状。
如图3(A)及(B)所示，袋装正极20具有如下构造，即，正极22由两片隔膜40夹持，并且两片隔膜40的缘部被接合。即，被组装(assembled)后的袋装正极20具有在袋状的一对隔膜40内收容有正极22的构造。
各隔膜40具有将由陶瓷(耐热材料)形成的耐热层(heat-resistantlayers)49分别涂覆在由树脂形成的隔膜层(separation layer)48的两面上的3层构造。即，在隔膜层48和正极22之间隔着耐热层49。本实施方式的隔膜40通过与耐热层49一体化而具有耐热性能(耐热性隔膜)。隔膜层48例如由聚乙烯、聚丙烯等聚烯烃类微多孔质树脂(polyolefin microporous resin)形成。
正极22通过将正极活性物质层(cathode active material layer)24分别形成在薄片状的正极集电体(cathode current collector)21(集电箔(current collector foil))的两面而构成。此外，在正极集电体21的正极耳片23上，未形成正极活性物质层24。
两片隔膜40在周缘上的接合部(fastened portions)42处彼此接合(熔接)而形成袋状(以下，也称为袋状隔膜(separator envelope)40)。因此，各隔膜40比正极22(除了正极耳片23之外)大。对于袋装正极20的制造方法进行后述。另外，从袋状隔膜40的直线状的一个边缘44A将正极耳片23引出，在与一个边缘44A相对的边缘44B上形成有局部凸出的结合部(joint portion)43。结合部43与外装材料13结合，其结果，电池要素15被固定在外装材料13上。
如图4所示，负极30通过将负极活性物质层34分别形成在薄片状的负极集电体31(集电箔)的两面而构成。此外，在负极集电体31的负极耳片33上，未形成负极活性物质层34。
如图5所示，发电要素15通过将负极30和袋装正极20交替地层叠而构成，在负极30和正极22之间隔着隔膜40。在图5中示出发电要素15的一个边缘(结合部43)的剖面，在将外装材料13封装时，隔膜40的结合部43被外装材料13夹持而结合。层叠后的正极耳片23与正极引线11结合，层叠后的负极耳片33与负极引线12结合(参照图2)。此外，在图5中，未表现出隔膜40的3层构造(隔膜层48及耐热层49)。负极30的负极活性物质层34形成为比正极22的正极活性物质层24大一圈(参照图5)。
由于作为将袋装正极20和负极30交替地层叠而制造锂离子二次电池的方法，采用公知的方法，因此省略对其工序的详细的说明。另外，在本实施方式中，由于本实施方式中的正极活性物质、负极活性物质、集电箔等采用锂离子二次电池所使用的公知的材料，因此省略对这些材料的详细说明。
(热熔接装置)
如图6(A)及(B)所示，热熔接装置100具有：工作台101，其载置工件；以及熔接单元110，其设置在工作台101的3个周缘上。工件是重叠有隔膜40、正极22、以及隔膜40的1组。熔接单元110位于比正极22更靠近外侧、且比隔膜40的周缘更靠近内侧的位置。熔接单元110具有用于将两片隔膜40夹持并加压·加热而进行热熔接的上熔接头111和下熔接头112。上熔接头111及下熔接头112中的至少一方(在本实施方式中仅上熔接头111)构成为可垂直移动。上熔接头111在工件的送入/送出时向上方避让，在熔接时上熔接头111朝着下熔接头112下降。其结果，压力被施加至作为两片隔膜40的接合部42的部分。此外，为了防止熔接时的工件的位置偏差，热熔接装置100也具有用于保持工件的保持件(未图示)。保持件只要是设置在不会妨碍熔接的位置即可，可以设置在任意位置处。
如图6(B)所示，在上熔接头111及下熔接头112上，与熔接位置(形成接合部42的位置：参照图3(A))相对应地设置有熔接片120。在本实施方式中，上熔接头111垂直地移动，下熔接头112不移动。因此，也可以在工作台101的周缘的与下熔接头112相当的位置处直接配置熔接片120(也可以将下熔接头112与工作台101进行组合)。
各熔接片120，整体例如由铜、不锈钢、铁等金属形成，并内置有发热体(电热器)。熔接片120通过发热体而使整体发热。在相对的熔接片120的至少一方(在本实施方式中，下熔接头112状的熔接片120)的表面，形成有凹凸面(rugged surface)125。
如图7(A)～(C)所示，在具有凹凸面125的熔接片120的表面(与隔膜40的抵接面)上，设置多个微小的凸部(minute protrusions)121而形成有凹凸面125。各凸部121的大小及高度、以及相邻的凸部121间的距离，对应于所要熔接的隔膜40的隔膜层48的厚度、耐热层49的厚度而变化。凸部121的高度至少大于或等于耐热层49的厚度，优选为大于或等于隔膜40的厚度。
凸部121的作用是施加压力而在微小区域上局部地破坏耐热层49，在后面对此进行叙述。因此，如果凸部121的高度至少大于或等于耐热层49的厚度，则再结合隔膜层48的柔软性(弹性)，凸部121会陷入(dig into)耐热层49，耐热层49被破坏。另外，如果凸部121的高度大于或等于隔膜40的厚度，则凸部121的陷入量变大，能够可靠地将耐热层49破坏。
此外，凸部121的高度在仅在一方的熔接片120形成凹凸面125(凸部121)的情况下没有限制，为隔膜40的厚度的2倍左右是足够的。其原因在于，在使一对熔接片120相对而夹持两片隔膜40时，由于被未形成凹凸面125的另一方的熔接片120的平坦表面支承，因此凸部121的钻入不会过量。
另一方面，在相对的一对熔接片120的双方上均形成凹凸面125(凸部121)、且凸部121的前端之间接触的情况下，基于相同的理由，对凸部121的高度没有限制。但是，在凸部121前端之间不接触的情况下，凸部121的高度需要限制为不会产生因钻入过量而引起隔膜40的断裂的高度。在该情况下，只要将相对的凸部121的各高度设为隔膜40的厚度左右，就不会使隔膜40断裂，能够可靠地仅破坏耐热层49。
另外，凸部121的前端(top end)不形成为尖锐的形状，而是形成为曲面形状(rounded shape)、倒角形状(chamfered shape)。凸部121的前端会使隔膜40变形，如果形成为尖锐的形状，则会使隔膜40损伤。因此，凸部121的前端形成为不会使隔膜40损伤的形状。
凸部121的平面形状在本实施方式中为长圆(对角部倒圆角的四边形)，但也可为圆或椭圆。对于凸部121的配置，如图7(A)所示，优选配置成长圆的凸部121在两个方向上(沿直角)彼此不同地配置(arranged in a bidirectionally(perpendicularly)staggered pattern)。追加详述，根据这种结构，能够将耐热层49破坏并且高效地将隔膜层48热熔接。
凸部121也可以形成为拱形形状的凸部(arch-shaped protrusions)、编织物表面形状的细小的凸部(woven-texture minute protrusions)、或者直线状的长的凸部(long straight protrusions)。另外，凹凸面125可以不由凸部121，而是例如由微小的圆形的球表面凹痕(minutecircular dimples)形成。
(袋装电极的制造方法)
对采用上述的热熔接装置100的袋装电极的制造方法的实施方式进行说明。如图8(A)及(B)所示，在本实施方式中，仅在下熔接头112的熔接片120上形成有凸部121。
首先，对隔膜40的构造和其接合部42进行补充。如图3(B)所示，隔膜40具有由隔膜层48和涂覆在该隔膜层48两面的耐热层49形成的3层构造。隔膜层48例如由聚烯烃类树脂形成。如周知所示，离子能够透过隔膜层48，但是隔膜层48不会流过电流。隔膜层48在130～180℃左右熔化。
另一方面，耐热层49例如由多孔质陶瓷形成。电解液能够透过耐热层49。重合后的隔膜40的隔膜层48由于耐热层49而不接触。耐热层49为绝缘体。耐热层49的耐热温度大于或等于800℃，即使是180℃左右的隔膜层48熔化的温度，耐热层49也不会熔化或变形。耐热层49防止由于因二次电池10的内部短路所产生的热量而熔融的隔膜层48的两侧的正极22和负极30的直接接触。
为了将正极20装袋而施加用于将两片隔膜40的缘部热熔接的热量，仅使隔膜层48熔融，但由于在两片隔膜40的隔膜层48之间存在耐热层49，因此缘部不会被熔接。另一方面，如果过度施加热量(热量过高或长时间加热)，则导致隔膜层48变质而不能够进行熔接。
因此，在本实施方式中，通过采用上述的热熔接装置100，通过具有凹凸面125的熔接片120进行加压，从而在微小区域将耐热层49破坏，并且施加热量而将隔膜层48熔接(被熔接的部分变为接合部42)。下面，对袋装电极的制造方法进行说明。
首先，如图8(A)所示，将按照隔膜40、正极22、及隔膜40的顺序层叠而成的工件置于工作台101上。通过上熔接头111及下熔接头112将位于比正极22更靠近外侧的两片隔膜40重叠的周缘部(重合部分)夹入并加压(图8(B)中的空心箭头P)。其结果，在被熔接片120加压的耐热层49的部分处，产生微小的破坏(断裂)，在耐热层49的破坏部分200处，两片隔膜40的隔膜层48接触。
加压后(或者与加压同时)将熔接片120加热而使隔膜层48熔融，隔膜层48通过破坏部分而被熔接。加热温度因隔膜层48材质而不同，在聚烯烃类树脂的情况下为130～180℃。在隔膜层48的树脂熔失之前，停止加热(使熔接片120分离)。如果隔膜层48固化，则接合结束，能够在周缘部将两片隔膜40可靠地接合。
对加压及加热的时期没有特别限定，优选在同时、或稍微先进行加压后进行加热。这样，在通过加压将耐热层49破坏的同时、或者在破坏之后，隔膜层48熔化而被熔接。此外，也可以先进行加热后再进行加压，在该情况下，在因加热而使隔膜层48的树脂熔失之前进行加压，在树脂消失之前停止加热(使熔接片120分离)。由此，能够将两片隔膜40接合。
[实施例]
在下面所说明的实施例中，将耐热层(陶瓷)49分别涂覆在隔膜层(聚烯烃类树脂)48的两面上所形成的两片隔膜40，通过形成有凹凸面125的熔接片120进行熔接。另外，在对比例中，通过未形成凹凸面125，而是具有平坦面的熔接片120将两片隔膜40熔接。
在第1实施例中，在下熔接头112的熔接片120的表面设置有微小的凸部121而形成凹凸面125。一片隔膜40的整体厚度为大约25μm。一片隔膜40的三层(一个隔膜层48及两个耐热层49)分别具有均等的厚度。各熔接片120的大小为4mm×2mm。形成凹凸面125的凸部121各自为长度0.25mm及宽度0.125mm的长圆形状。凸部121(长圆形)的中心的间隔S(参照7(A))为0.4mm。
下面，对隔膜40的熔接工序进行说明。
(1)将利用隔膜40夹持正极22的工件配置在规定位置。
(2)工件被保持在接合部42(被熔接的部分)以外的位置。
(3)在比正极22更靠近外侧、且隔膜40的周缘内侧(将两片隔膜40直接层叠的位置)，利用一对熔接片120将工件夹入并进行加压。加压是通过能够破坏耐热层49的程度的压力而进行的。
(4)将上熔接头111及下熔接头112的熔接片120加热。加热温度为180℃。
(5)在接合部42形成穿孔、或接合部42熔失之前，使上熔接头111的熔接片120离开隔膜40，使加热结束(至穿孔、熔失为止的时间是根据经验(实验)获得的)。
(6)将上述(2)中的保持解除。
利用光学显微镜及电子显微镜对按照上述方式作成的袋装正极20的接合部42进行观察。图9(A)是接合部42的光学显微镜照片。图9(B)是图9(A)中的ⅠXB部分(熔接部分)的电子显微镜照片。图9(C)是将图9(B)中的IXC部分进一步放大后的电子显微镜照片，图9(D)是IXD部分进一步放大后的电子显微镜照片。
如图9(A)～图9(D)所示，利用设置有微小的凸部121的凹凸面125，将耐热层49局部破坏(破坏部分200：参照8(B))，在破坏部分200处，由树脂形成的隔膜层48彼此熔接(特别是参照图9(D))。
另外，作为熔接部分(IXB部分)整体，如图9(B)所示，存在有耐热层49已被破坏的部分(参照图9(C))和耐热层49未被破坏的部分(参照图9(D))。因此，首先，将图9(C)所示的耐热层49未被破坏的部分作为样品而切出，进行了两片隔膜40的剥离强度试验。剥离强度试验，如图10所示，利用卡盘300将熔接部分(接合部42)的两侧保持，使熔接部分剥离。
剥离试验的结果为，在耐热层49未被破坏的部分的样品中，以0.02N使两片隔膜40分离。另一方面，将接合部42整体作为样品而切出，进行了相同的剥离强度试验。在该情况下，以0.2～0.4N使两片隔膜40分离。因此，通过将耐热层49局部破坏，使隔膜层48局部地熔接，从而能够作为接合部42整体而获得足够的接合强度。
如上所述，通过对隔膜层48所涂覆的耐热层49施加压力并进行加热，从而能够使两片隔膜40的由树脂形成的隔膜层48彼此接触而形成熔接部。
图11(A)是上述的第1实施例所涉及的接合部42的表面(下熔接头112侧的表面)的电子显微镜照片，图11(B)是激光显微镜照片。如图11(A)及图11(B)所示，在利用第1实施例的熔接片120而被熔接的接合部42的表面上，形成有纵向及横向的压痕。压痕在接合部42的表面形成有凹凸(asperity)。上述压痕的特征在于保持有均匀的间隔而进行配置，使耐热层49的破坏部分200的碎片向周围移动，破坏部分200被接合(熔接)。
下面，对能够实现与上述的第1实施例相同的效果的第2实施例进行说明。在本实施例中，在熔接片120的平坦面上安装金属网130而形成有凹凸面125。图12是安装有金属网130的熔接片120的表面的激光显微镜照片。
在本实施例中，也是仅在设置于下熔接头112的熔接片120上安装有金属网130(形成有凹凸面125)。金属网130的金属线的波形成有微小的凸部121。在本实施例中，也制作了袋装正极20(隔膜40的接合部42)，并且与第1实施例相同地进行了接合部42整体的剥离强度试验。图13是示出剥离试验的结果的图表(拉伸量-拉伸强度)。图表中的线a表示加压后的加热时间为2秒的样品的试验结果，线b表示加热时间为7秒的样品的试验结果。样品的结构、其他条件与第1实施例相同。
如图13所示，在采用了金属网130的情况下，在加热时间为2秒的试验中，能够获得0.3～0.6N的足够的剥离强度，在加热时间为7秒的试验中，能够获得0.2～1.0N的足够的剥离强度。并且，在对网眼的大小进行改变的过程中，可知对于形成高剥离强度的接合部42，网眼的大小优选为40筛眼/英寸。另外，可知对于形成剥离强度稍弱的、但难以穿孔的接合部42，优选为60筛眼/英寸。对于金属网130向熔接片120的安装，能够通过焊锡焊接、熔接而进行。
下面，对第3实施例进行说明。在本实施例中，改变熔接片120的材质，与第1实施例相同地，制作了袋装正极20(隔膜40的接合部42)。可知在熔接片120为热传导率高的铜制的情况下，虽然剥离强度高，但剥离强度基于凸部121的间隔S或加压力的变动大，在接合部42处易于穿孔。另一方面，可知在熔接片120为热传导率低的不锈钢(SUS)制的情况下，难于穿孔。根据这些情况，熔接片120的凸部121的大小、熔接温度、熔接时间等条件，优选为考虑熔接片120的材质而适当地设定。
下面，对第4实施例进行说明。在本实施例中，在安装在第2实施例中的下熔接头112的熔接片120上的金属网130上，还安装有聚四氟乙烯(PTFE：polytetrafluoroethylene)树脂膜(耐热膜)胶带(以下，简称为PTFE胶带)。此外，在下熔接头112的具有平坦面的熔接片120的表面也安装有PTFE胶带。图14是安装有PTFE胶带135的熔接片120的放大剖面图。PTFE胶带135的厚度为0.08～0.23mm。
PTFE胶带135的热传导率比金属低。因此，即使延长熔接时间也不会发生穿孔。其原因在于，利用PTFE胶带135对熔融的隔膜层48和熔接片120的熔接进行了抑制。由此，与第2实施例的情况相比，能够进行长时间加热而提高熔接強度。另外，PTFE胶带135也具有吸收冲击的效果，熔接片120对隔膜40的加压也可以更大，这也使熔接强度提高。
下面，对第5实施例进行说明。在本实施例中，通过在下熔接头112的熔接片120的表面形成球表面凹痕(dimples)140而形成有凹凸面125。图15是形成有球表面凹痕140的熔接片120的俯视图。如图15所示，在熔接片120的表面(与隔膜40的接触面)，按规律地配置有球表面凹痕140。根据本实施例，也获得了与第1实施例相同程度的剥离强度。
另外，作为其他实施例，具有将凸部121形成为马蹄形状、长圆形状，按压面积比上述第1实施方式大的凸部121，即使采用与隔膜40的接触面积大的熔接片120，也能够形成具有足够的剥离强度的接合部42。在图16(A)～图16(D)中示出上述的实施例的接合部42中的压痕的光学显微镜照片。图16(A)示出通过金属网130而形成有凹凸面125的第1实施例。图16(B)示出通过球表面凹痕140而形成有凹凸面125的第5实施例。图16(C)示出通过马蹄形状的凸部121而形成有凹凸面125的实施例。图16(D)示出通过长圆形状的凸部121而形成有凹凸面125的实施例。无论在哪种情况下，都在接合部42的表面上形成有压痕，将隔膜40可靠地接合(熔接)。
此外，如果熔接时间、熔接温度不适当，则不能获得良好的熔接。如果熔接温度大于等于200℃，则隔膜层48的熔融过度地进行，不能够形成接合部42。另外，由于隔膜层48熔融而缩短，因此会导致产生翘曲、折皱。因此，熔接温度优选为小于200℃。
另外，如果熔接时间长，则接合部42的强度变大，但产生隔膜40向熔接片120的附着、穿孔及折皱的增大。对于厚度25μm的隔膜40的熔接，如果与熔接片120的接触时间大于或等于0.3秒，则会发生穿孔。因此，熔接时间优选为小于0.3秒。
如上所述，优选对应于隔膜层48的材质及厚度、熔接片120的材质以及凸部121的大小等，适当设定最佳的熔接条件。
[对比例]
为了比较，采用未形成凹凸面125的平坦面的熔接片120，也对将不具有耐热层的仅由1层隔膜层构成的隔膜熔接而成的样品进行了剥离试验。图17(A)及图17(B)是对比例所涉及的接合部42(也包括不能够进行接合的情况)的表面的光学显微镜照片。如图17(A)所示，在隔膜40的耐热层49上产生局部龟裂，虽然隔膜层49熔化，但是无法将两片隔膜40接合(熔接)。
在进一步延长熔接时间后，如图17(B)所示，由于熔失·断裂而穿孔。隔膜40的一部分附着在熔接片120上而穿孔。取代熔接时间，在将温度进一步升高后(略微超过200℃的温度)，熔失而穿孔，无法将两片隔膜40接合(熔接)。另外，如果进一步加大压力，则穿孔而无法将两片隔膜40接合(熔接)。在对温度、压力留有富裕的情况下的孔，与如图17(B)所示的孔大体相同。
(1)根据上述实施方式(实施例)，在通过熔接片120的凹凸面125而被加压的隔膜40的重合部分中，通过凹凸面125而被加压的耐热层49被破坏。破坏后的耐热层49被加热，加热部分的隔膜层48熔融。其结果，隔膜层48的熔融的树脂和耐热层49的碎片混合而被接合(熔接)，形成接合部42。通过接合部42，袋状电极(在上述实施方式中为袋状正极20)的两片隔膜40的周缘部能够可靠地被接合(熔接)。
(2)设置在熔接片120的凹凸面125上的凸部121的各前端，形成为曲面形状、倒角形状。由此，在对隔膜40进行夹持并加压时，不会导致将隔膜40弄破。
(3)采用了安装金属网130而形成凹凸面125的熔接片120。由此，将作用在隔膜40上的压力分散，能够不将隔膜40切断而使其变形。
(4)采用在凹凸面125的表面具有热传导率比金属低的树脂膜的熔接片120。由此，能够抑制热量急剧地传递至隔膜40(特别是由树脂形成的隔膜层48)。因此，即使延长熔接时间，也不会穿孔。另外，利用树脂膜的弹性力，缓和加压时的载荷，即使增大加压力，也能够防止在耐热层49产生大的龟裂。
(5)通过使加热温度小于200℃，能够以低能量进行熔接，能够防止由树脂形成的隔膜层48的碳化、蒸发。
(6)采用在隔膜层48的至少一方的表面上预先形成有耐热层49的隔膜40。由此，与隔膜层48和耐热层49为单独部件的情况相比，在制作袋装电极(袋装正极)20时，在对隔膜40-正极22-隔膜40进行层叠时，易于进行输送等操作。另外，易于进行层叠工序，能够减少层叠工时。
(7)特别地，采用在隔膜层48的两面上预先形成有耐热层49的隔膜40。由此，能够提高对在发生内部短路的情况下的因热量引起的隔膜层48的熔融进行防止的效果。另外，易于进行层叠工序，能够进一步减少层叠工时。
(8)对于袋装电极20，在上述的重合部分中，耐热层49被破坏，在该破坏部分200处形成隔膜层48被接合而成的接合部42。因此，在采用该袋装电极20而制造二次电池10时，易于进行袋装电极20的操作。另外，在对采用该袋装电极20的二次电池10进行操作时，也能够将袋装电极20内的电极22可靠地保持。
(9)在上述接合部42的表面，形成具有凹凸的压痕。因此，仅通过观察，就能够可靠地判断隔膜40已接合(熔接)。
(10)采用上述(8)或(9)的袋装电极20而形成二次电池10的发电要素15。因此，在施加振动时，袋装电极20内的电极22实际上受到特别的保持。因此，该二次电池10适于用作电动汽车、混合动力汽车的驱动用电源。能够提供一种二次电池10，即，即使向搭载于汽车上的二次电池施加振动，该二次电池也能够耐振动。
(11)在熔接装置100中，在上述的袋装电极20的制造中所利用的至少一对熔接片120中的至少一方的表面上形成有凹凸面125。由此，在由熔接片120的凹凸面125加压后的隔膜40的重合部分中，由凹凸面125加压后的耐热层49被破坏。将被破坏的耐热层49加热，使加热部分的隔膜层48熔融。其结果，熔融的隔膜层48的树脂和耐热层49的碎片混合而被接合(熔接)，形成接合部42。通过接合部42，袋状电极(在上述实施方式中为袋状正极20)的两片隔膜40的周缘部能够可靠地被接合(熔接)。
(12)在熔接装置100中，凹凸面125具有多个凸部121，各凸部121的前端形成为曲面形状或倒角形状。因此，在夹持隔膜40而进行加压时，不会导致将隔膜40破坏。
(13)在熔接装置100中，由金属网130形成凹凸面125。因此，能够将作用在隔膜40上的压力分散，不将隔膜40切断而使其变形。
(14)在熔接装置100中，所述凹凸面125在其表面具有耐热性膜。由此，能够抑制热量急剧地传递至隔膜40(特别是由树脂形成的隔膜层48)。因此，即使延长熔接时间，也不会穿孔。另外，利用耐热性膜的弹性力，缓和加压时的载荷，即使增大加压力，也能够防止在耐热层49产生大的龟裂。
(15)在熔接装置100中，加热温度小于200℃。由此，能够以低能量进行熔接，能够防止由树脂形成的隔膜层48的碳化、蒸发。
本发明并不限定于上述的实施方式(实施例)。例如，袋装电极在上述实施方式中为袋装正极20，也可以为收容有负极30的袋装负极。
另外，在上述实施方式中，隔膜40具有(耐热层49-隔膜层48-耐热层49)的3层构造，但也可以具有仅在隔膜层48的单面形成有耐热层49的2层构造。耐热层49的作用如上述所，防止内部短路时的正极22和负极30的直接接触。因此，即使将采用了上述2层构造的隔膜40的袋装正极20和负极30层叠(或者，将袋装负极和正极层叠)，也能够使耐热层49存在于正极22和负极30之间。
在采用2层构造的隔膜40的情况下，在接合部42中，以使至少一个耐热层49存在于隔膜层48之间的方式，将两片隔膜40接合(熔接)。即，以两片隔膜40的至少一方的耐热层49与内部的电极接触的方式，制作袋装电极。
此外，作为具有耐热层的隔膜，为了防止因发热而引起的隔膜层48的熔融，如上述的实施方式所示，更优选在由树脂形成的隔膜层48的两面形成有耐热层49的3层构造的隔膜40。
在上述实施方式中，隔着间隔而形成有多个接合部42。熔接片120设置成与接合部42的位置及大小相匹配。但是，接合部42的位置及大小并不限定于上述实施方式。例如，长的熔接片120也可以沿着隔膜40的周围而设置。
在上述实施方式中，耐热层是被涂覆在隔膜层的表面而形成的。但是，也可以使分别独立地制作的隔膜层和耐热层彼此接合而形成隔膜。在该情况下，在制作袋装电极时，也可以在使隔膜层、耐热层及电极重合之后，将周缘接合(熔接)。即，在制作袋装电极的同时，将隔膜层和耐热层接合而形成隔膜。由此，采用已有的(不具有耐热层的)隔膜层，能够制作具有耐热层的袋装电极。
在上述第4实施例中，在金属网130上安装有树脂膜。同样地，通过将热传导率低的树脂膜安装在未采用金属网130的凹凸面125的表面上，也能够实现与第4实施例相同的效果。除了上述的变形例，本发明基于权利要求书所记载的结构，能够进行各种变形，这些变形例当然也在本发明的范围内。
在此，日本国专利申请第2012-4211号(2012年1月12日申请)的全部内容通过参照而引入本说明书中。通过参照本发明的实施方式，如上述所示对本发明进行了说明，但本发明并不限定于上述的实施方式。本发明的范围依照权利要求书而确定。

Claims (15)

1.一种袋装电极的制造方法，在该方法中，
将电极配置在由树脂形成的两个隔膜层之间，
将耐热层配置在所述两个隔膜层中的至少一个和所述电极之间，
将所述两个隔膜层、所述电极及所述耐热层进行层叠，
在与所述电极相比的外侧，利用一对熔接片夹持隔着所述耐热层而重合的所述两个隔膜层的重合部分而进行加压及加热，
使加压及加热后的所述重合的部分中的所述耐热层破坏，将所述两个隔膜层接合。
2.根据权利要求1所述的袋装电极的制造方法，在该方法中，
在所述一对熔接片中的至少一个的表面上，形成具有多个凸部的凹凸面，
所述多个凸部的各前端形成为曲面形状或倒角形状。
3.根据权利要求2所述的袋装电极的制造方法，在该方法中，
所述凹凸面由金属网形成。
4.根据权利要求2或3所述的袋装电极的制造方法，在该方法中，
所述凹凸面在其表面上具有热传导率比金属低的树脂膜。
5.根据权利要求1至4中任一项所述的袋装电极的制造方法，在该方法中，
所述加热的温度小于200℃。
6.根据权利要求1至5中任一项所述的袋装电极的制造方法，在该方法中，
所述耐热层预先形成在所述两个隔膜层中的所述至少一个的表面上。
7.根据权利要求1至6中任一项所述的袋装电极的制造方法，在方法中，
所述耐热层分别形成在所述两个隔膜层各自的两面上。
8.一种袋装电极，其具有：
由树脂形成的两个隔膜层；
电极，其配置在所述两个隔膜层之间；以及
两个耐热层，它们分别配置在所述两个隔膜层和所述电极之间，
在与所述电极相比的外侧，在隔着所述耐热层而重合的所述两个隔膜层的重合部分中，所述耐热层被破坏而形成有将所述两个隔膜层接合的接合部。
9.根据权利要求8所述的袋装电极，其中，
在所述接合部的表面上形成具有凹凸的压痕。
10.一种二次电池，
其具有发电要素，该发电要素是使权利要求8或9所述的袋装电极、和极性与所述袋装电极的极性不同的电极层叠而形成的。
11.一种热熔接装置，
其具有在权利要求1至7中任一项所述的袋装电极的制造方法中所利用的至少一对熔接片，
在所述至少一对熔接片中的至少一个的表面上，形成有凹凸面。
12.根据权利要求11所述的热熔接装置，其中，
所述凹凸面具有多个凸部，
所述多个凸部的各前端形成为曲面形状或倒角形状。
13.根据权利要求11所述的热熔接装置，其中，
所述凹凸面由金属网形成。
14.根据权利要求11至13中任一项所述的热熔接装置，其中，
所述凹凸面在其表面上具有耐热树脂膜。
15.根据权利要求11至14中任一项所述的热熔接装置，其中，
所述加热的温度小于200℃。
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