CN106159124A - 蓄电设备用外装构件和使用了该外装构件的蓄电设备 - Google Patents
蓄电设备用外装构件和使用了该外装构件的蓄电设备 Download PDFInfo
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Abstract
本发明涉及一种蓄电设备用外装构件和使用了该外装构件的蓄电设备。所述蓄电设备用外装构件依次至少具有基材层、粘接层、金属箔层、防腐蚀处理层、粘接树脂层和热熔融粘合树脂层,其中,粘接层的厚度为0.3~3μm,金属箔层的所述基材层侧的表面的十点平均粗糙度Rzjis(根据JIS B0601)为0.3~3μm,粘接层的厚度为所述十点平均粗糙度Rzjis以上并且为3μm以下,基材层与金属箔层的剥离粘接强度(根据JIS K6854‑3)为5~12N/15mm。
Description
技术领域
本发明涉及蓄电设备用外装构件和使用了该外装构件的蓄电设备。
背景技术
近年来,作为电脑、手机等可移动末端装置、摄像机、卫星、车辆等中使用的蓄电设备,大力开发了能够实现超薄型化、小型化的蓄电设备。作为上述的蓄电设备中使用的外装构件,由多层膜形成的层压外装构件(例如基材层/第1粘接层/金属箔层/第2粘接层/热熔融粘合树脂层这样的构成)得到了关注。由多层膜形成的层压外装构件与以往的作为容器使用的金属制的罐不同,在重量轻、散热性高、能够自由选择形状方面,都比金属制的罐优良。
蓄电设备例如可通过下述方法来形成:在多层膜的蓄电设备用外装构件的一部分上通过冷成型而形成凹部,在该凹部内装入正极、隔膜、负极和电解液等,将外装构件的剩余部分折回并覆盖凹部,将外装构件的边缘部分通过热熔融粘合而密封在一起。近年来,为了能够有效地收纳更多的内容物而提高能量密度,还制造了在贴合的蓄电设备用外装构件的两侧形成了凹部的蓄电设备。可是,如果加深凹部,则用模具进行成型加工时,拉伸率较高的部位即凹部的边和角的部分容易发生针孔或断裂。
为了解决上述问题,进行了下述尝试:使用双轴拉伸聚酰胺等膜作为蓄电设备用外装构件的基材层来保护金属箔,抑制针孔、断裂(例如,专利文献1:日本特许3567230号公报)。
可是,专利文献1的技术的现状是,成型加工时依然有可能观察到针孔或断裂的发生、基材层从金属箔层的剥离等。
发明内容
因此,本发明鉴于上述问题,目的是提供一种通过具有充分的成型性从而能够抑制基材层的保护效果的下降的蓄电设备用外装构件。本发明的另一目的是提供使用了该外装构件的蓄电设备。
本发明的蓄电设备用外装构件依次至少具有基材层、粘接层、金属箔层、防腐蚀处理层、粘接树脂层和热熔融粘合树脂层,其中,粘接层的厚度为0.3~3μm,金属箔层的基材层侧的表面的十点平均粗糙度Rzjis(根据JIS B0601)为0.3~3μm,粘接层的厚度为该十点平均粗糙度Rzjis以上并且为3μm以下,基材层与金属箔层的剥离粘接强度(根据JIS K6854-3)为5~12N/15mm。
上述的外装构件由于具有充分的成型性,所以能够抑制基材层的保护效果的下降。此外,这里所说的基材层的保护效果是指成型加工时防止在金属箔层发生针孔、断裂等的效果,为了确保该效果,优良的成型性是必要的。发明人们认为,如果粘接层变厚,则不能充分获得基材层的针孔抑制效果,成型性下降,另一方面,当减薄粘接层时,该层本身变得容易断裂,成型性下降。
本发明中,优选的是,基材层的厚度X与粘接层的厚度Y之比X/Y为4~50。由此,基材层的保护效果提高,成型性提高。
本发明中,优选的是,粘接层由使含有2官能以上的芳香族系或脂肪族系异氰酸酯的固化剂与含有多元醇的主剂作用的双组分固化型的聚氨酯系粘接剂形成。其中,主剂的羟基与固化剂的异氰酸酯基的当量比([NCO]/[OH])优选为1~50。由此,可以进一步提高粘接层的成型加工时的追随性。
本发明中,优选的是,基材层含有聚酰胺膜和聚酯膜之中的至少一者。由此,基材层的保护效果提高,成型性提高。
本发明中,优选的是,基材层含有隔着第2粘接层层叠的聚酰胺膜和聚酯膜,第2粘接层由与上述粘接层相同的粘接剂形成,第2粘接层的厚度为0.3~3μm。由此,基材层的保护效果提高,成型性提高。
本发明中,优选的是,基材层的金属箔层侧的面被实施了电晕处理、火焰处理、等离子体处理或紫外线照射处理。由此,粘接层的追随效果提高。
本发明中,优选的是,在粘接层与金属箔层之间进一步具有第2防腐蚀处理层。由此,粘接层的追随效果提高。
本发明的蓄电设备具有:具有正极和负极的蓄电设备单元;与正极和负极各自连接的金属端子;和收纳所述蓄电设备单元的具有深度为6mm以上的成型加工部的外装构件,其中,外装构件是上述本发明的蓄电设备用外装构件,外装构件是通过以热熔融粘合树脂层成为内面的方式被折回并且端部被加压热熔融粘合,从而将所述蓄电设备单元密封并且将金属端子以其一部分露出到外部的方式夹持。使用了本发明的蓄电设备用外装构件的蓄电设备中,作为保护层的基材层充分发挥作用,能够显现优良的电解液耐受性等。另外,该设备由于能够有效地收纳更多的内容物,所以能够提高能量密度。
根据本发明,可以提供一种通过具有充分的成型性从而能够抑制基材层的保护效果的下降的蓄电设备用外装构件。另外,根据本发明,可以提供使用了该外装构件的蓄电设备。此外,根据使用了本发明的蓄电设备用外装构件的蓄电设备,能够有效地收纳更多的内容物,从而提高能量密度。
附图说明
图1是本发明的一个实施方式的蓄电设备用外装构件的剖面图。
图2是表示本发明的一个实施方式的蓄电设备的制作方法的工序图。
图3是本发明的另一个实施方式的蓄电设备用外装构件的剖面图。
图4是本发明的另一个实施方式的蓄电设备用外装构件的剖面图。
符号说明
1,3,4外装构件、2蓄电设备、11基材层、11A,11B基材膜、12粘接层、13金属箔层、14防腐蚀处理层、15粘接树脂层、16热熔融粘合树脂层、17第2粘接层、18第2防腐蚀处理层、21蓄电设备单元、22成型加工部、23引线、24极耳密封层、25极耳、26加压热熔融粘合部、27折回部。
具体实施方式
以下,示出本发明的蓄电设备用外装构件(以下称作“外装构件1”)和使用了该外装构件的蓄电设备(以下称作“蓄电设备2”)的实施方式的一个例子来进行详细说明。
如图1所示,本实施方式的外装构件1具有按照下述顺序依次至少层叠了基材层11、粘接层12、金属箔层13、防腐蚀处理层14、粘接树脂层15和热熔融粘合树脂层16而成的层叠结构。
(基材层11)
基材层11赋予制造蓄电设备时的密封工序中的耐热性,起到抑制加工或流通时有可能发生针孔的作用。另外,还起到防止成型加工时的金属箔层13的断裂、防止金属箔层13与其它的金属接触的绝缘性等作用。
作为基材层11,可以列举出例如聚酯树脂、聚酰胺树脂、聚烯烃树脂等拉伸或未拉伸膜等。其中,从提高成型性、耐热性、耐刺穿性、绝缘性的观点出发,优选双轴拉伸聚酰胺膜或双轴拉伸聚酯膜。
基材层11可以是由1片膜构成的单一膜,也可以是将2片以上的膜用干式层压粘接剂贴合而形成的复合膜。
当基材层11是单一膜时,可以使用作为单层单一膜的双轴拉伸聚酰胺膜或双轴拉伸聚酯膜、或作为多层单一膜的聚酰胺/聚酯热塑性弹性体/聚酯的双轴拉伸共挤出膜。另外,当基材层11是复合膜时,可以使用将2片膜用干式层压粘接剂贴合而成的多层复合膜的双轴拉伸聚酰胺膜/聚氨酯系粘接剂/双轴拉伸聚酯膜。
当基材层11是复合膜时,可以列举出如图3所示那样基材膜11A(例如聚酰胺膜)和基材膜11B(例如聚酯膜)隔着第2粘接层17层叠而形成的构成。第2粘接层17优选由与后述的粘接层12相同的粘接剂形成。另外,第2粘接层17的厚度优选为0.3~3μm、更优选为0.5~2μm。通过将第2粘接层设定成上述的构成,使用复合膜时的成型加工性会提高,而且可以防止成型加工时层叠的膜之间的剥离。
基材层11的金属箔层13侧的面优选实施了电晕处理、火焰处理、等离子体处理或紫外线照射处理。通过实施上述处理,基材层11表面被活化而具有极性的官能团增加,所以基材层11表面与粘接层12的反应成分容易发生交联反应。因此,粘接层12的追随基材层11的效果进一步提高。
此外,还可以在基材层11内部分散或在表面涂布阻燃剂、滑爽剂、抗粘连剂、抗氧化剂、光稳定剂、增粘剂、防静电剂等添加剂。
作为滑爽剂,可以列举出脂肪酸酰胺(例如油酸酰胺、芥酸酰胺、硬脂酸酰胺、山萮酸酰胺、亚乙基双油酸酰胺、亚乙基双芥酸酰胺等)等。
作为抗粘连剂,优选二氧化硅等各种填料系的抗粘连剂。添加剂可以单独使用1种,也可以并用2种以上。
从耐刺穿性、绝缘性、成型加工性等的观点出发,基材层11的厚度优选为6~50μm、更优选为10~40μm。基材层11的厚度如果为6μm以上,则耐针孔性、绝缘性提高,基材层11的厚度如果为50μm以下,则相对于厚度的成型性提高。
为了改善耐擦伤性和滑爽性等,可以在基材层11的表面形成凹凸形状。
(粘接层12)
粘接层12形成于基材层11与金属箔层13之间。粘接层12具有将基材层11和金属箔层13牢固地粘接所必要的密合力(粘附力)。另外,粘接层12具有追随性以为了保护不会由成型加工时的基材层11引起金属箔层13的断裂。
作为粘接层12,可以使用以聚酯多元醇、聚醚多元醇、丙烯酸多元醇等为主剂、以2官能以上的芳香族系或脂肪族系异氰酸酯为固化剂的双组分固化型粘接剂来形成。此外,固化剂的异氰酸酯基(NCO基)相对于主剂的羟基(OH基)的当量比([NCO]/[OH])优选为1~50、更优选为3~40。[NCO]/[OH]如果为1以上,则容易获得良好的粘接性。另外,[NCO]/[OH]如果大于50,则由于交联反应过剩地进行,所以粘接层12容易变脆变硬。因此,容易发生粘接层12的断裂,难以追随基材层11和金属箔层13。
粘接层12中可以添加热塑性弹性体、增粘剂、填料、颜料、染料等。
粘接层12的厚度优选为0.3~3μm、更优选为0.5~2μm。粘接层12的厚度低于0.3μm时,由于粘接层12内的微小的裂纹或针孔等缺陷等而使得粘接层12容易发生断裂,成型加工时难以获得良好的追随性。另一方面,粘接层12的厚度超过3μm时,成型加工时基材层11不能保护金属箔层13,成型性下降。
粘接层12的厚度为金属箔层13的基材层11侧的表面的十点平均粗糙度Rzjis以上并且为3μm以下,优选为该十点平均粗糙度Rzjis+0.5μm以上并且为2.5μm以下。厚度低于金属箔层13的基材层11侧的表面的十点平均粗糙度Rzjis时,粘接剂会进入到金属箔层13的表面凹凸的槽中,产生粘接剂层变薄的部分,成型加工时有可能无法获得追随性。另一方面,厚度超过3μm时,成型加工时基材层11不能保护金属箔层13,成型性下降。
基材层11的厚度X与粘接层12的厚度Y之比X/Y优选为4~50、更优选为6~30。通过将X/Y设定为4以上,成型加工时容易获得基材层11保护金属箔层13的效果。另一方面,X/Y超过50时,该保护效果难以提高,而且由于基材层的膜厚变厚,所以会成为成本增加和制作的蓄电设备的能量密度下降的原因。
基材层11与金属箔层13之间的根据JIS K6854-3测得的剥离粘接强度为5~12N/15mm、优选为6~10N/15mm、更优选为7~8N/15mm。剥离粘接强度低于5N/15mm时,成型加工时粘接层12有可能不能追随基材层11和金属箔层13而剥离,由此无法获得基材层11的保护效果,成型性下降。另一方面,剥离粘接强度超过12N/15mm时,为了提高剥离粘接强度而有必要使粘接层12硬化,有可能导致粘接层12的追随性下降,成型性受到损害。作为提高剥离粘接强度的方法,当使用上述的双组分固化型粘接剂来形成粘接层12时,可以列举出下述的方法等方法:使用羟基值较高的主剂;使用NCO含量较高的固化剂和反应性较高的固化剂;增大固化剂的NCO基相对于主剂的OH基的当量比([NCO]/[OH]);增加基材层11或金属箔层13的粘接层12侧的表面的官能团数;使金属箔层13与基材层11粘接后在适当的条件下进行老化(养护)处理。
(金属箔层13)
金属箔层13形成于粘接层12与粘接树脂层15之间。金属箔层13具有防止水分浸入蓄电设备内的水蒸气阻隔性。另外,金属箔层13具有延展性以便进行深冲成型。
作为金属箔层13,可以使用铝或铝合金、不锈钢、无氧铜、韧铜、磷脱氧铜、黄铜、磷青铜、电解铜、镍、铁镍合金等。调质处理的种类可以考虑各金属的伸长量来选择。其中,作为金属箔层13,从重量(比重)、防湿性、加工性、成本方面考虑,优选铝箔。作为铝箔,可以使用公知的软质铝箔,从耐针孔性和成型时的延展性的观点出发,优选含有铁的铝箔。铝箔(100质量%)中的铁的含量是相对于铝箔的总质量100质量%优选为0.1~9.0质量%、更优选为0.5~2.0质量%。铁的含量如果为下限值以上,则耐针孔性、延展性提高。铁的含量如果为上限值以下,则柔软性提高。
金属箔层13的厚度优选为20~80μm、更优选为25~60μm。当金属箔层13的厚度低于20μm时,有可能产生针孔或断裂;另一方面,当金属箔层13的厚度超过80μm时,设备的性能并不会格外提高,相反会成为成本增加和能量密度下降的原因。
金属箔层13的基材层11侧的表面的十点平均粗糙度Rzjis(根据JIS B0601)优选为0.3~3μm、更优选为1~2.5μm。十点平均粗糙度Rzjis低于0.3时,与粘接层12的密合力变得不充分,成型加工时基材层11有可能无法保护金属箔层13。另一方面,金属箔层13的表面的十点平均粗糙度Rzjis超过3μm时,由于粘接剂填充金属箔的槽,形成了粘接剂较薄的部分,成型加工时有可能不能追随。
对金属箔层13的表面还可以进行用金属微粒修饰等用于提高密合力的各种处理。
(防腐蚀处理层14)
防腐蚀处理层14形成于金属箔层13的热熔融粘合树脂层16侧。防腐蚀处理层14例如对于锂离子蓄电设备来说,可防止因电解质与水分的反应所产生的氢氟酸而引起的金属箔层13表面的腐蚀。另外,防腐蚀处理层14除了具有防腐蚀功能以外,还具有作为与粘接树脂层15的锚定层的功能。防腐蚀处理层14的形成中可以使用例如下述处理:利用了由铬酸盐、磷酸盐、氟化物和各种热固性树脂形成的防腐蚀处理剂的铬酸盐处理、利用了由稀土类元素氧化物(例如氧化铈等)、磷酸盐、各种热固性树脂形成的防腐蚀处理剂的氧化铈溶胶处理等。作为防腐蚀处理层14,只要是能够赋予金属箔层13耐腐蚀性的被膜即可,不限于由上述处理形成的被膜,例如也可以是使用磷酸盐处理、勃姆石处理等而形成的被膜。另外,防腐蚀处理层14不限于是单层,也可以采用例如下述的2层以上的构成等:在具有防腐蚀功能的被膜上涂布树脂作为保护层。
从防腐蚀功能和作为锚定层的功能的观点出发,防腐蚀处理层14的厚度优选为5nm~1μm、更优选为10~200nm。
防腐蚀处理层也可以形成于金属箔层13的基材层11侧。即,如图4所示那样,也可以在金属箔层13与粘接层12之间设置第2防腐蚀处理层18。通过设置第2防腐蚀处理层18,不仅能够防止从外部对金属箔层13的腐蚀,该层还可以作为锚定层起作用,因此粘接层12对金属箔层13的追随性提高。第2防腐蚀处理层18可以使用在防腐蚀处理层14中列举的防腐蚀处理剂来形成。
在基材层11与金属箔层13之间,除了粘接层12以外,还可以进一步含有上述的第2防腐蚀处理层18和用于分担基材层11的功能的层(例如,防止加工、流通时发生受伤的耐伤层、防止金属箔层13与外部部件电接触的绝缘层)等层。本实施方式中,从维持良好的成型性的观点出发,即使在设置了上述那些层的情况下,基材层与金属箔层之间所含的层的厚度也优选为0.3~3μm、更优选为0.5~2μm。此外,如图1所示,当基材层11与金属箔层13之间仅仅含有粘接层12时,基材层11与金属箔层13之间所含的层的厚度即是粘接层12的厚度。另外,如图4所示,当基材层11与金属箔层13之间含有粘接层12和第2防腐蚀处理层18时,基材层11与金属箔层13之间所含的层的厚度即是粘接层12和第2防腐蚀处理层18的厚度。
(粘接树脂层15)
粘接树脂层15是将热熔融粘合树脂层16和金属箔层13进行粘接的层。粘接树脂层15的形成方法大致分为两类,可以采用热层压或干式层压。
在通过挤出层压来形成粘接树脂层15的热层压的情况下,作为其成分,优选热塑性树脂,例如可以列举出聚烯烃系树脂、弹性体树脂、将聚烯烃系树脂进行酸改性而得到的酸改性聚烯烃系树脂。作为聚烯烃系树脂,可以列举出例如低密度、中密度、高密度的聚乙烯;乙烯-α-烯烃共聚物、均聚、嵌段或无规聚丙烯、丙烯-α-烯烃共聚物、或它们的酸改性物等。作为酸改性聚烯烃,可以列举出例如聚烯烃被不饱和羧酸或其酸酐以及衍生物酸改性后的产物等。作为不饱和羧酸或其酸酐以及衍生物,可以列举出例如丙烯酸、甲基丙烯酸、马来酸、富马酸、巴豆酸、衣康酸以及它们的酸酐、单酯和二酯、酰胺、酰亚胺等。其中,优选丙烯酸、甲基丙烯酸、马来酸、马来酸酐,特别优选马来酸酐。不饱和羧酸或其酸酐以及衍生物只要与聚烯烃共聚即可,作为其形式,可以列举出嵌段共聚、无规共聚、接枝共聚等。上述那些不饱和羧酸或其酸酐以及衍生物可以单独使用1种,也可以并用2种以上。
聚烯烃系树脂和酸改性聚烯烃系树脂具有优良的电解液耐受性。另外,作为弹性体树脂,可以列举出SEBS(聚苯乙烯/聚乙烯/聚丁烯/聚苯乙烯)、SBS(聚苯乙烯/聚丁二烯/聚苯乙烯)、SEPS(聚苯乙烯/聚乙烯/聚丙烯/聚苯乙烯)、SEP(聚苯乙烯/聚乙烯/聚丙烯)、SIS(聚苯乙烯/聚异戊二烯/聚苯乙烯)共聚物等。通过在酸改性聚烯烃系树脂中添加上述弹性体树脂,也能够得到改善从对由冷成型时的裂纹所引起的拉伸白化耐受性、由浸润性改善得到的密合力、由各向异性降低所带来的制膜性、热熔融粘合强度等特性。
另一方面,在干式层压的情况下,粘接树脂层15可以使用在粘接层12中列举的双组分固化型粘接剂等来形成。
在热层压的情况下,粘接树脂层15的厚度优选为8~30μm,更优选为10~20μm。粘接树脂层15的厚度如果为8μm以上,则容易获得充分的粘接强度,如果为30μm以下,则容易减少从密封端面透过到蓄电设备内部的水分量。
在干式层压的情况下,粘接树脂层15的厚度优选为1~5μm。粘接树脂层15的厚度如果低于1μm,则密合力下降,所以难以获得层压强度,粘接树脂层15的厚度如果超过5μm,则由于膜变厚而容易发生膜破裂。粘接树脂层15的厚度为1~5μm时,可以使热熔融粘合树脂层16与金属箔层13牢固地密合。
(热熔融粘合树脂层16)
热熔融粘合树脂层16隔着粘接树脂层15形成于金属箔层13上。通过例如使2片外装构件的热熔融粘合树脂层16彼此之间相对向,在热熔融粘合树脂层16的熔融温度以上进行加压热熔融粘合,从而能够将内容物密封于外装构件内部。作为热熔融粘合树脂层16,可以列举出使用聚烯烃树脂形成的树脂层。作为聚烯烃树脂,可以列举出低密度、中密度、高密度的聚乙烯、均聚、嵌段或无规聚丙烯等。另外,还可以列举出使前述树脂与丙烯酸或甲基丙烯酸等极性分子共聚而得到的共聚物、交联聚烯烃等聚合物等,可以采用实施了分散、共聚等而得到的树脂。上述聚烯烃树脂可以单独使用1种,也可以并用2种以上。热熔融粘合树脂层16也可以使用混合有前述的各种树脂而得到的膜来形成。另外,热熔融粘合树脂层16可以是单层膜,也可以是多层膜。
热熔融粘合树脂层16中还可以含有滑爽剂、抗粘连剂、抗静电剂、成核剂、颜料、染料等各种添加剂。上述的添加剂可以单独使用1种,也可以并用2种以上。上述那些添加剂可以被含有在热熔融粘合树脂层16中,也可以涂布于热熔融粘合树脂层16的与金属箔层13侧相反一侧的表面。此外,作为滑爽剂,可以使用在基材层11中列举的那些滑爽剂。通过使滑爽剂含有在热熔融粘合树脂层16中、或者将滑爽剂如上所述地涂布于热熔融粘合树脂层16的表面,可以提高成型性。
热熔融粘合树脂层16的厚度优选为20~90μm。厚度低于20μm时,难以确保充分的层压强度,超过90μm时,水蒸气的透过量容易变多。
[外装构件1的制作方法]
以下,对上述的外装构件1的制造方法进行说明。作为外装构件的制造方法,可以列举出例如具有下述工序(1-1)~(1-3)的方法。
工序(1-1):在金属箔层13的一个面上形成防腐蚀处理层14。
工序(1-2):在金属箔层13的未形成防腐蚀处理层14的面上,隔着粘接层12通过干式层压法贴合基材层11,制作层叠体(防腐蚀处理层14/金属箔层13/粘接层12/基材层11)。
工序(1-3):在金属箔层13的形成了防腐蚀处理层14的面上,隔着粘接树脂层15贴合热熔融粘合树脂层16,制作外装构件1(热熔融粘合树脂层16/粘接树脂层15/防腐蚀处理层14/金属箔层13/粘接层12/基材层11)。
工序(1-1)
在金属箔层13的一个面上涂布防腐蚀处理剂后,进行烘烤而形成防腐蚀处理层14。此时,还可以不仅仅对一个面,而是对两个面都进行防腐蚀处理,进一步形成第2防腐蚀处理层18。防腐蚀处理剂的涂布方法没有特别限定,例如可以列举出凹版涂布法、凹版逆向涂布法、辊涂法、逆向辊涂法、模涂法、棒涂法、吻涂法、逗号刮刀式涂布法等。
工序(1-2)
在金属箔层13的未形成防腐蚀处理层14的面(或者,形成了第2防腐蚀处理层18的面)上,隔着粘接层12使用干式层压法贴合基材层11,制作层叠体(防腐蚀处理层14/金属箔层13/粘接层12/基材层11)。粘接层12的涂布方法没有特别限定,例如可以列举出凹版涂布法、凹版逆向涂布法、辊涂法、逆向辊涂法、模涂法、棒涂法、吻涂法、逗号刮刀式涂布法等。在工序(1-2)中,为了促进固化反应和结晶的稳定化,优选在20~100℃的范围内进行老化(养护)处理。低于20℃时,固化反应的促进效果较差,超过100℃时,基材层11会劣化,成型性容易下降。
工序(1-3)
粘接树脂层15的形成方法大致分为使用热层压的方法和使用干式层压的方法。
采用热层压时,可以进一步选择干式工艺或湿式工艺。
在干式工艺的情况下,在前述层叠体的金属箔层13(形成了防腐蚀处理层14的面)上挤出层压粘接树脂,再层叠通过吹塑法或T型模挤出法得到的用于形成热熔融粘合树脂层16的膜。然后,为了提高金属箔层13与热熔融粘合树脂层16的密合性,还可以实施热处理(老化处理、热层合等)。另外,也可以用吹塑法或T型模挤出法制作层叠了粘接树脂层15和热熔融粘合树脂层16而成的多层膜,将该多层膜通过热层合层叠于前述层叠体上,从而隔着粘接树脂层15在金属箔层13上层叠热熔融粘合树脂层16。
在湿式工艺的情况下,将酸改性聚烯烃系树脂等粘接树脂的分散型的粘接树脂液涂布于前述层叠体的金属箔层13(形成有防腐蚀处理层14的面)上,在粘接树脂的熔点以上的温度下使溶剂挥发,使粘接树脂熔融软化并进行烘烤后,将热熔融粘合树脂层16通过热层合等热处理进行层叠。
在采用干式层压的情况下,在前述层叠体的金属箔层13(形成了防腐蚀处理层14的面)上涂布粘接树脂层15,用烘箱进行加热,使溶剂干燥。然后,通过干式层合将热熔融粘合树脂层16进行热压粘,从而制作外装构件1。粘接树脂层15的涂布方法没有特别限定,例如可以列举出凹版涂布、凹版逆向涂布、辊涂法、逆向辊涂法、模涂法、棒涂法、吻涂法、逗号刮刀式涂布法等。在工序(1-3)中,为了促进固化反应和结晶的稳定化,优选在20~100℃的范围内进行老化(养护)处理。低于20℃时,固化反应的促进效果较差,超过100℃时,基材层11会劣化,成型性容易下降。
通过以上说明的工序(1-1)~(1-3)得到了外装构件1。此外,外装构件1的制造方法不限于依次实施前述工序(1-1)~(1-3)的方法。例如,也可以在工序(1-2)之前进行工序(1-3)。
[蓄电设备的制作方法]
本实施方式的蓄电设备具有:具有正极和负极的蓄电设备单元;与正极和负极各自连接的金属端子;和收纳所述蓄电设备单元的具有成型加工部的外装构件,其中,外装构件是通过以热熔融粘合树脂层成为内面的方式被折回并且端部被加压热熔融粘合,从而将所述蓄电设备单元密封并且将金属端子以其一部分露出到外部的方式夹持。
更具体地说,本实施方式的蓄电设备2如图2所示具有下述构造:由外装构件1收纳蓄电设备单元21,并且用加压热熔融粘合部26夹持分别与蓄电设备单元21的正极和负极连接的由引线23和极耳密封层24构成的极耳25。
以下,使用图2对蓄电设备2的制造方法进行说明。作为蓄电设备2的制造方法,可以列举出例如具有下述工序(2-1)~(2-4)的方法。
工序(2-1):在外装构件1的一半的区域上形成用于配置蓄电设备单元21的成型加工部22(参照图2(a)和图2(b))。
工序(2-2):在外装构件1的成型加工部22上配置蓄电设备单元21。然后将外装构件1的另一半的区域以使热熔融粘合树脂层成为内面的方式折回而使3边重合,仅将夹持由引线23和极耳密封层24构成的极耳25的1边进行加压热熔融粘合(参照图2(b)和图2(c))。
工序(2-3):留下剩余2边中的1边并进行加压热熔融粘合,然后从留下的1边注入电解液,在真空状态下进行加压热熔融粘合(参照图2(c))。
工序(2-4):将夹持极耳25的1边以外的边的加压热熔融粘合部26端部切掉,将加压热熔融粘合部26沿着成型加工部22弯折(参照图2(d))。
工序(2-1)
以使外装构件1的热熔融粘合树脂层16侧达到所期望的成型深度的方式用模具进行成型。作为成型方法,使用具有外装构件1的总厚以上的缝隙的阴模和阳模所构成的模具,从热熔融粘合树脂层16侧向基材层11侧进行深冲成型,从而得到具有所期望的深冲量的外装构件1。如果具有追随性较高的粘接层12,并使用成型性较高的外装构件1,则能够进行更深的成型,所以可以获得能够收纳很多蓄电设备单元21的能量密度较高的蓄电设备2。本实施方式中,成型加工部22的成型深度如果为6mm以上,则能够高效地收纳蓄电设备单元21,能够提高能量密度。从上述观点出发,该成型深度优选为8mm以上。此外,从防止成型加工使得金属箔层13变得过薄的观点出发,该成型深度的上限可以设定为12mm左右。
工序(2-2)
在外装构件1的成型加工部22内放入由正极、隔膜、负极等构成的蓄电设备单元21,将与正极和负极接合的极耳25从成型加工部22引出到外部。然后,将外装构件1的热熔融粘合树脂层16彼此重叠,并将夹持外装构件1的极耳25的边进行加压热熔融粘合。加压热熔融粘合可以通过温度、压力、时间这3个条件来控制,在热熔融粘合树脂层16的熔融温度以上使其切实地熔融,并在适度压力的条件下进行。
工序(2-3)
然后,留下夹持极耳25的边以外的1边,同样地进行加压热熔融粘合。然后,从留下的1边注入溶解有电解质的电解液,经历了老化下的脱气工序之后,为了避免空气进入到内部,在真空状态下进行最终加压热熔融粘合。
工序(2-4)
将夹持引线23的边以外的加压热熔融粘合边端部切掉,除去从端部露出的热熔融粘合树脂层16。然后,将加压热熔融粘合部26折回至成型加工部22侧,形成折回部27,由此得到蓄电设备2。
通过以上说明的工序(2-1)~(2-4)得到了蓄电设备2。不过,蓄电设备2的制造方法不限于以上记载的方法。例如,也可以省略工序(2-4)。
以上,参照着附图对本发明的实施方式进行了详述,但具体的构成并不限于上述实施方式,也包括不超出本发明的要旨的范围的设计变更等。
实施例
以下,通过实施例详细说明本发明,但本发明不受以下记载的限定。
[使用材料]
本实施例中使用的材料如下所示。
(基材层11)
基材A-1:聚酯膜。(厚度为9μm)。
基材A-2:聚酯膜。(厚度为12μm)。
基材A-3:聚酯膜。(厚度为15μm)。
基材A-4:聚酯膜。(厚度为25μm)。
基材A-5:聚酰胺膜。(厚度为12μm)。
基材A-6:聚酰胺膜。(厚度为15μm)。
基材A-7:聚酰胺膜。(厚度为25μm)。
基材A-8:聚酯膜。(厚度为12μm)。对粘接层侧进行电晕处理。
基材A-9:聚酯膜。(厚度为12μm)。对粘接层侧进行火焰处理。
基材A-10:聚酯膜。(厚度为12μm)。对粘接层侧进行等离子体处理。
基材A-11:聚酰胺膜(厚度为12μm)/第2粘接层(厚度为0.3μm)/聚酯膜(厚度为12μm)的层叠膜。将聚酰胺膜与粘接层侧粘接。第2粘接层使用粘接剂B-6。
基材A-12:聚酰胺膜(厚度为12μm)/第2粘接层(厚度为3μm)/聚酯膜(厚度为12μm)的层叠膜。将聚酰胺膜与粘接层侧粘接。第2粘接层使用粘接剂B-6。
基材A-13:聚酰胺膜(厚度为12μm)/第2粘接层(厚度为5μm)/聚酯膜(厚度为12μm)的层叠膜。将聚酰胺膜与粘接层侧粘接。第2粘接层使用粘接剂B-6。
(粘接层12)
粘接剂B-1:双组分固化型聚酯型聚氨酯粘接剂。(由聚酯多元醇和聚异氰酸酯形成的双组分固化型粘接剂。[NCO]/[OH]=0.5)
粘接剂B-2:双组分固化型聚酯型聚氨酯粘接剂。(由聚酯多元醇和聚异氰酸酯形成的双组分固化型粘接剂。[NCO]/[OH]=1)
粘接剂B-3:双组分固化型聚酯型聚氨酯粘接剂。(由聚酯多元醇和聚异氰酸酯形成的双组分固化型粘接剂。[NCO]/[OH]=3)
粘接剂B-4:双组分固化型聚酯型聚氨酯粘接剂。(由聚酯多元醇和聚异氰酸酯形成的双组分固化型粘接剂。[NCO]/[OH]=10)
粘接剂B-5:双组分固化型聚酯型聚氨酯粘接剂。(由聚酯多元醇和聚异氰酸酯形成的双组分固化型粘接剂。[NCO]/[OH]=20)
粘接剂B-6:双组分固化型聚酯型聚氨酯粘接剂。(由聚酯多元醇和聚异氰酸酯形成的双组分固化型粘接剂。[NCO]/[OH]=40)
粘接剂B-7:双组分固化型聚酯型聚氨酯粘接剂。(由聚酯多元醇和聚异氰酸酯形成的双组分固化型粘接剂。[NCO]/[OH]=50)
粘接剂B-8:双组分固化型聚酯型聚氨酯粘接剂。(由聚酯多元醇和聚异氰酸酯形成的双组分固化型粘接剂。[NCO]/[OH]=70)
粘接剂B-9:双组分固化型聚醚型聚氨酯粘接剂。(由聚醚多元醇和聚异氰酸酯形成的双组分固化型粘接剂。[NCO]/[OH]=20)
粘接剂B-10:双组分固化型丙烯酸型聚氨酯粘接剂。(由丙烯酸多元醇和聚异氰酸酯形成的双组分固化型粘接剂。[NCO]/[OH]=20)
(第2防腐蚀处理层18)
处理剂C-1:由铬酸盐形成的处理层。(层厚为100nm)。
处理剂C-2:由氧化铈形成的处理层。(层厚为100nm)。
(金属箔层13)
金属箔D-1:铝箔8021材。(厚度为40μm、基材层侧的表面的十点平均粗糙度Rzjis为0.3μm)
金属箔D-2:铝箔8079材。(厚度为40μm、基材层侧的表面的十点平均粗糙度Rzjis为0.6μm)
金属箔D-3:不锈钢箔304材。(厚度为40μm、基材层侧的表面的十点平均粗糙度Rzjis为0.7μm)
金属箔D-4:韧铜箔C1100材。(厚度为40μm、基材层侧的表面的十点平均粗糙度Rzjis为1.1μm)
金属箔D-5:电解铜箔。(厚度为40μm、基材层侧的表面的十点平均粗糙度Rzjis为2.5μm)
金属箔D-6:电解铜箔。(厚度为40μm、基材层侧的表面的十点平均粗糙度Rzjis为8.0μm)
金属箔D-7:表面研磨过的铝箔8021材。(厚度为40μm、基材层侧的表面的十点平均粗糙度Rzjis为0.2μm)
(防腐蚀处理层14)
处理剂E-1:由氧化铈形成的处理层。(层厚为100nm)。
(粘接树脂层15)
粘接树脂F-1:马来酸酐改性聚丙烯系树脂。(层厚为20μm)。
(热熔融粘合树脂层16)
热熔融粘合树脂G-1:聚丙烯膜。(层厚为40μm)。
(外装构件的制作)
在金属箔D-1~D-7的一个面上用直接凹版涂布法形成防腐蚀处理层E-1。在实施例24、25中,在未形成防腐蚀处理层E-1的金属箔D-1的另一面上,用直接凹版涂布法形成防腐蚀处理层C-1或C-2。然后,对于金属箔D-1~D-7,在未形成防腐蚀处理层E-1的面上,分别涂布粘接剂B-1~B-10中的任一个,用干式层压法贴付基材A-1~A-13中的任一个。然后,除比较例6之外,在40℃下进行7天老化。然后,在得到的各层叠体的防腐蚀处理层E-1侧用挤出装置挤出粘接树脂F-1而形成粘接层后,再贴合膜G-1并进行夹芯层合,从而形成密封层。经过以上的工序,制作各实施例和比较例的外装构件。
[各种评价]
按照以下的方法进行各种评价。评价结果示于表1和表2中。
[剥离粘接强度的评价]
将各个例子中所制作的外装构件切成15mm×100mm的尺寸,测定基材层与金属箔层的根据JIS K6854-3测得的15mm宽度下的剥离粘接强度。在剥离粘接强度的评价时,在基材层断裂的情况下,将断裂时的强度作为剥离粘接强度。
[成型性的评价]
将各个例子中所制作的外装构件切成150mm×190mm的坯料形状,在室温为23℃、露点温度为-35℃的成型环境下一边使成型深度变化一边进行冷成型,评价成型性。作为冲头,使用形状为100mm×150mm、角部圆角半径(RCP)为1.5mm、冲头肩半径(RP)为0.75mm、模肩半径(RD)为0.75mm的冲头。按照以下基准进行评价,将评价D记为不良。
“A”:能够未发生断裂、裂纹地进行成型深度为6mm以上的深冲成型。
“B”:能够未发生断裂、裂纹地进行成型深度为4mm以上但小于6mm的深冲成型。
“C”:能够未发生断裂、裂纹地进行成型深度为3mm以上但小于4mm的深冲成型。
“D”:成型深度小于3mm的深冲成型下发生了断裂、裂纹。
[成型时剥离的评价]
在成型性的评价时,对基材层与金属箔层之间是否发生剥离进行评价。评价按照以下的基准来进行,将评价B记为不良。
“A”:在成型性的评价时,在基材层与金属箔层之间未发生剥离。
“B”:在成型性的评价时,在基材层与金属箔层之间发生了剥离。
表1
表2
如表1和表2所示,本实施例中,成型加工时无基材层的剥离,而且粘接层的追随性也被充分确保。即,可以认为,本实施例的蓄电设备用外装构件通过具有充分的成型性,从而能够抑制基材层的保护效果的下降。
与之对照,比较例中均不能获得充分的成型性。例如在比较例1、2、9和10中,由于粘接层的厚度较薄、成型加工时不能获得追随性,所以无法得到充分的成型性;另一方面,在比较例3~5和11~13中,由于粘接层的厚度较厚、基材层不能防止金属箔层的针孔或断裂,所以成型性下降。另外,剥离粘接强度过低或过高的比较例6~8也不能获得充分的成型性。另外,比较例6中,由于金属箔层的表面粗糙度较小,密合性不充分,所以无法获得成型性。比较例7和比较例8中,由于金属箔层的粗糙度较大,所以粘接层被埋没,无法获得充分的密合力。
Claims (8)
1.一种蓄电设备用外装构件,其依次至少具有基材层、粘接层、金属箔层、防腐蚀处理层、粘接树脂层和热熔融粘合树脂层,其中,
所述粘接层的厚度为0.3~3μm,
所述金属箔层的所述基材层侧的表面的根据JIS B0601测得的十点平均粗糙度Rzjis为0.3~3μm,所述粘接层的厚度为所述十点平均粗糙度Rzjis以上并且为3μm以下,
所述基材层与所述金属箔层的根据JIS K6854-3测得的剥离粘接强度为5~12N/15mm。
2.根据权利要求1所述的蓄电设备用外装构件,其中,所述基材层的厚度X与所述粘接层的厚度Y之比X/Y为4~50。
3.根据权利要求1或2所述的蓄电设备用外装构件,其中,所述粘接层由使含有2官能以上的芳香族系或脂肪族系异氰酸酯的固化剂与含有多元醇的主剂作用的双组分固化型的聚氨酯系粘接剂形成,所述主剂的羟基与所述固化剂的异氰酸酯基的当量比[NCO]/[OH]为1~50。
4.根据权利要求1~3中任一项所述的蓄电设备用外装构件,其中,所述基材层含有聚酰胺膜和聚酯膜之中的至少一者。
5.根据权利要求4所述的蓄电设备用外装构件,其中,所述基材层含有隔着第2粘接层层叠的所述聚酰胺膜和所述聚酯膜,
所述第2粘接层由与所述粘接层相同的粘接剂形成,所述第2粘接层的厚度为0.3~3μm。
6.根据权利要求1~5中任一项所述的蓄电设备用外装构件,其中,在所述粘接层与所述金属箔层之间进一步具有第2防腐蚀处理层。
7.根据权利要求1~6中任一项所述的蓄电设备用外装构件,其中,所述基材层的所述金属箔层侧的面被实施了电晕处理、火焰处理、等离子体处理或紫外线照射处理。
8.一种蓄电设备,其具有:
具有正极和负极的蓄电设备单元;
与所述正极和所述负极各自连接的金属端子;和
收纳所述蓄电设备单元的具有深度为6mm以上的成型加工部的外装构件,
所述外装构件是权利要求1~7中任一项所述的蓄电设备用外装构件,
所述外装构件是通过以所述热熔融粘合树脂层成为内面的方式被折回并且端部被加压热熔融粘合,从而将所述蓄电设备单元密封并且将所述金属端子以其一部分露出到外部的方式夹持。
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