CN112335098A - 蓄电装置用封装材料以及使用了该封装材料的蓄电装置 - Google Patents
蓄电装置用封装材料以及使用了该封装材料的蓄电装置 Download PDFInfo
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- CN112335098A CN112335098A CN201980041950.XA CN201980041950A CN112335098A CN 112335098 A CN112335098 A CN 112335098A CN 201980041950 A CN201980041950 A CN 201980041950A CN 112335098 A CN112335098 A CN 112335098A
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Abstract
本发明的一个方面涉及的蓄电装置用封装材料具有层叠结构,该层叠结构依次具备:基材层、第一粘接层、金属箔层、第二粘接层、以及含有聚酯系树脂的内层。内层在160~280℃的范围内具有利用差示扫描量热仪所测定的熔解时的熔解峰值温度。基材层具有比内层的熔解峰值温度高的熔解峰值温度。
Description
技术领域
本发明涉及蓄电装置用封装材料以及使用了该封装材料的蓄电装置。
背景技术
作为蓄电装置,已知有(例如)锂离子电池、镍氢电池及铅蓄电池等二次电池、以及双电层电容器等电化学电容器。因便携设备的小型化或设置空间的限制等,要求蓄电装置的进一步小型化,因此能量密度高的锂离子电池备受关注。作为锂离子电池所使用的封装材料,一直以来使用金属制罐体,但逐渐改用轻量、散热性高且能够以低成本制作的多层膜。
将上述多层膜用于封装材料的锂离子电池称为层压型锂离子电池。通过使封装材料覆盖电池内容物(正极、隔板、负极、电解液等),防止水分向内部渗入。就层压型的锂离子电池而言,例如可以通过以下方法制造:在封装材料的一部分中通过冷成型形成凹部,将电池内容物容纳于该凹部内,并将封装材料的其余部分折回并用热封来密封周缘部分(例如,参照专利文献1)。
现有技术文献
专利文献
专利文献1:日本特开2013-101765号公报
发明内容
本发明要解决的课题
但是,作为锂离子电池的新一代电池,正在进行被称为全固态电池的蓄电装置的研究开发。全固态电池具有不使用有机电解液而使用固态电解质作为电解物质的特征。锂离子电池不能在高于电解液的沸点温度(80℃左右)的温度条件下使用,与此相对,全固态电池可以在超过100℃的温度条件下使用,同时,能够通过在高温条件下(例如100~150℃)工作来提高锂离子的传导性。
然而,在使用上述那样的层叠体作为封装材料来制造层压型的全固态电池的情况下,由于封装材料的耐热性不充分,可能导致全固态电池的封装的密封性不充分。另外,本发明人在尝试提高封装材料的耐热性的时候发现,具有层叠结构的封装材料中,由于基材层(外侧的层)与内层(具有热封性的层)的组合,蓄电装置(特别是热封部)的外观变差。
本发明是鉴于上述课题而完成的,提供用于制造具有优异外观的蓄电装置且耐热性优异的封装材料、以及使用了该封装材料的蓄电装置。
用于解决课题的手段
本发明的一个方面提供蓄电装置用封装材料。该封装材料具有层叠结构,该层叠结构依次具备:基材层、第一粘接层、金属箔层、第二粘接层、以及含有聚酯系树脂的内层,内层在160~280℃的范围内具有利用差示扫描量热仪(DSC)所测定的熔解时的熔解峰值温度,基材层具有比内层的熔解峰值温度高的熔解峰值温度。作为聚酯系树脂的具体例子,可以列举出聚对苯二甲酸乙二醇酯(PET)及其共聚物、以及以PET的成分为基础的聚酯系树脂。
现有的蓄电装置用封装材料的密封层(内层)主要由聚丙烯系树脂构成,熔点为130~150℃左右。因此,例如,当用于温度可达到100~150℃的全固态电池时,其耐热性不充分。与此相对,在本发明涉及的封装材料中,通过采用含有聚酯系树脂且在160~280℃的范围内具有熔解峰值温度的内层,在耐热性方面上也可适用于可达到上述温度的蓄电装置。另外,通过使基材层具有比内层的熔解峰值温度高的熔解峰值温度,能够抑制热封时因基材层(外侧的层)熔解而导致的外观变差。需要说明的是,这里所说的“熔解峰值温度”可以根据JIS K 7121-1987所记载的方法来求出,并且在独立出现2个以上熔解峰的情况下,采用最低的熔解峰值温度。
作为能够应用本发明涉及的封装材料的蓄电装置,可以列举出全固态电池。但是,不限于此,也可以将该封装材料应用于其他蓄电装置(例如,锂离子二次电池)中。
本发明涉及的封装材料的内层可以为单层结构,也可以为多层结构。在内层为单层结构的情况下,例如,内层可以是结晶性PET膜(熔解峰值温度:约255℃),也可以是因其中一部分不定形化而导致熔解峰值温度降低到(例如)160~250℃范围内的PET或其共聚物膜。熔解峰值温度降低了的膜也可以是以PET的成分为基础的聚酯系树脂的膜。这种聚酯系树脂具有源自乙二醇的结构单元、源自对苯二甲酸的结构单元、以及其他结构单元。作为成为该聚酯系树脂的结构单元的来源的二元醇成分,可以列举出新戊二醇、1,4-丁二醇、二乙二醇等。作为成为该聚酯系树脂的结构单元的来源的酸成分,可以列举出间苯二甲酸、己二酸、癸二酸等。通过调整这些结构单元的量,可以调整聚酯系树脂的熔点。以下,PET的共聚物以及以PET的成分为基础的上述聚酯系树脂称为PET系树脂。
在内层为多层结构的情况下,内层可以设为这样的构成:具备含有聚酯系树脂且熔解峰值温度为170~280℃的第一层、以及形成在第一层内侧的表面上且含有聚酯系树脂的第二层,第二层的熔解峰值温度在160~270℃的范围内且比第一层的熔解峰值温度低。通过采用比第一层更容易熔解的第二层,可以实现更优异的密封强度。从可以实现更优异的密封强度和耐热性的观点来看,第二层也可以采用含有热固性树脂的层。
在内层是具备第一层和第二层的多层结构的情况下,还可以进一步具备在第一层的与形成有第二层的一侧相反的那一侧的表面上所形成的第三层。第三层可以设为这样的构成:含有聚酯系树脂,并且熔解峰值温度在160~270℃的范围内且比第一层的熔解峰值温度低。通过采用比第一层更容易熔解的第三层,可以实现更优异的密封强度。从可以实现更优异的密封强度和耐热性的观点来看,第三层也可以采用含有热固性树脂的层。
本发明的一个方面提供一种蓄电装置(例如全固态电池),该蓄电装置具备:蓄电装置主体、从蓄电装置主体延伸出来的电流输出端子、以及夹持着电流输出端子且容纳蓄电装置主体的上述封装材料。
发明效果
根据本发明,提供了用于制造具有优异外观的蓄电装置且耐热性优异的封装材料、以及使用了该封装材料的蓄电装置。
附图简要说明
[图1]图1是表示本发明涉及的蓄电装置的一个实施方式的全固态电池的透视图。
[图2]图2是示意性地表示封装材料的一个实施方式的剖面图。
[图3]图3(a)~(c)是示意性地表示内层的构成的剖面图。
[图4]图4是图1所示的IV-IV线方向的剖面图,并且为示意性地表示全固态电池型的极耳(端子用树脂膜以及金属端子)的构成的图。
[图5]图5(a)~(c)为示意性地表示端子用树脂膜的构成的剖面图。
具体实施方式
以下,参照附图对本发明的实施方式进行详细地说明。需要说明的是,附图中,对于相同或相当的部分标注同一符号并省略重复的说明。另外,附图的尺寸比例不限于图示的比例。
<蓄电装置>
图1是表示本实施方式涉及的蓄电装置的示意性构成的透视图。在图1中,列举并图示了全固态电池作为蓄电装置100的一个例子,并进行以下说明。需要说明的是,具备图1所示构成的蓄电装置有时被称为电池组或电池单元。
蓄电装置100为全固态电池,其具备蓄电装置主体10、封装材料20、一对金属端子30(电流输出端子)、以及端子用树脂膜40(极耳密封件)。蓄电装置主体10是进行充放电的电池主体。封装材料20以覆盖蓄电装置主体10的表面并且与端子用树脂膜40的一部分接触的方式来配置。
<封装材料>
图2是表示封装材料20的剖面的一个例子的剖面图。封装材料20具有多层结构,该多层结构从外侧向内侧(蓄电装置主体10一侧)依次具备:基材层11、第一粘接层12a、第一防腐蚀处理层13a、阻隔层(金属箔层)15、第二防腐蚀处理层13b、第二粘接层12b、以及内层18。然后,内层18含有聚对苯二甲酸乙二醇酯(PET)或其共聚物,并且在160~280℃的范围内具有熔解峰值温度。基材层11具有比内层18的熔解峰值温度高的熔解峰值温度。
通过使内层18含有PET或其共聚物,并且在160~280℃的范围内具有熔解峰值温度,从而封装材料20可以实现在(例如)100~150℃的温度条件下所使用的蓄电装置100(全固态电池)的封装材料所需要的耐热性。另外,通过使基材层11具有比内层18的熔解峰值温度高的熔解峰值温度,从而能够抑制热封时因基材层11(外侧的层)熔解而导致的外观变差。以下,首先对内层18和基材层11进行说明。
内层18可以使用市售的结晶性PET膜(熔解峰值温度:约255℃)。根据内层18所需要的耐热性(蓄电装置100的工作温度条件等),可以在上述范围内调整内层18的熔解峰值温度,例如可以调整结晶性PET膜的结晶度,使其无延展性,形成包含聚对苯二甲酸乙二醇酯单元与其他树脂单元的共聚物,使用包含结晶性PET与无定形PET的PET膜。或者,可以使用以PET的成分为基础的聚酯系树脂作为内层18的材料。这种聚酯系树脂具有源自乙二醇的结构单元、源自对苯二甲酸的结构单元、以及其他结构单元。作为成为该聚酯系树脂的结构单元的来源的二元醇成分,可以列举出新戊二醇、1,4-丁二醇、二乙二醇等。作为成为该聚酯系树脂的结构单元的来源的酸成分,可以列举出间苯二甲酸、己二酸、癸二酸等。通过调整这些结构单元的量,可以调整聚酯系树脂的熔点。以下,将PET的共聚物以及以PET的成分为基础的上述聚酯系树脂称为PET系树脂。
如上所述,内层18的熔解峰值温度在160~280℃的范围内。当该温度小于160℃时,内层18的耐热性不充分,当超过280℃时,热封时所需要的温度过高。内层18的熔解峰值温度的下限可以为175℃、185℃、195℃、200℃、215℃、215℃、225℃或235℃。内层18的熔解峰值温度的上限可以为275℃、268℃、262℃或252℃。
内层18可以为单层结构,也可以为多层结构。如图3(a)所示,在内层18为单层结构的情况下,例如,内层18可以为结晶性PET膜(熔解峰值温度:约255℃),并且可以通过调整结晶性PET膜的结晶度、使其无延展性、使用PET系树脂,从而使其熔解峰值温度降低到(例如)160~250℃的范围内。需要说明的是,在将熔解峰值温度降低了的PET膜用作内层18的情况下,可以使用结晶性PET膜(熔解峰值温度:约255℃)作为基材层11。
在内层18为单层结构的情况下,内层18的厚度优选为10~100μm,更优选为20~80μm。通过使内层18的厚度为10μm以上,易于确保密封性和绝缘性,另一方面,通过使其为100μm以下,可以实现低成本化。
如图3(b)所示,内层18也可以为双层结构,其具有第一层18a、以及形成在第一层18a的内侧的表面上的第二层18b。第一层18a优选含有PET和/或PET系树脂且熔解峰值温度为170~280℃。第二层18b优选含有PET和/或PET系树脂且具有比第一层18a的熔解峰值温度低的熔解峰值温度。第二层18b的熔解峰值温度例如可以在160~270℃的范围内。第一层18a的熔解峰值温度TA与第二层18b的熔解峰值温度TB之间的差(TA-TB)优选为10℃以上,更优选为20~100℃。通过使该温度差为10℃以上,可以实现更优异的密封强度。
第一层18a的厚度优选为5~500μm,更优选为20~200μm。通过使第一层18a的厚度为5μm以上,易于确保绝缘性,另一方面,通过使其为500μm以下,可以实现低成本化。
从耐热性和密封强度的观点来看,第二层18b也可以使用含有热固性树脂的材料以替代PET或PET系树脂,也可以是含有PET或PET系树脂以及热固性树脂这两者的材料。作为热固性树脂,可以列举出聚酰亚胺树脂、酚醛树脂、尿素树脂、三聚氰胺树脂、不饱和聚酯树脂、氨基甲酸酯树脂、丙烯酸树脂、环氧树脂、呋喃树脂以及有机硅树脂。这些当中,可以单独使用一种,也可以并用两种以上。
第二层18b的厚度优选为5~500μm,更优选为20~200μm。通过使第二层18b的厚度为5μm以上,易于确保绝缘性,另一方面,通过使其为500μm以下,可以实现低成本化。
如图3(c)所示,内层18也可以为三层结构,其具有第一层18a、第二层18b、以及在第一层18a的与形成有第二层18b的一侧相反的那一侧的表面上所形成的第三层18c。第三层18c优选含有PET和/或PET系树脂且具有比第一层18a的熔解峰值温度低的熔解峰值温度。第三层18c的熔解峰值温度例如可以在160~270℃的范围内。第一层18a的熔解峰值温度TA与第三层18c的熔解峰值温度TC之间的差(TA-TC)优选为10℃以上,更优选为20~100℃。通过使该温度差为10℃以上,可以实现更优异的密封强度。
从耐热性和密封强度的观点来看,第三层18c也可以使用含有热固性树脂的材料以替代PET或PET系树脂,也可以是含有PET或PET系树脂以及热固性树脂这两者的材料。作为热固性树脂,可以列举出聚酰亚胺树脂、酚醛树脂、尿素树脂、三聚氰胺树脂、不饱和聚酯树脂、氨基甲酸酯树脂、丙烯酸树脂、环氧树脂、呋喃树脂以及有机硅树脂。这些当中,可以单独使用一种,也可以并用两种以上。
第三层18c的厚度优选为5~500μm,更优选为20~200μm。通过使第三层18c的厚度为5μm以上,易于确保高的密封强度,另一方面,通过使其为500μm以下,可以实现低成本化。需要说明的是,上述第二层18b与第三层18c可以是相同的构成,也可以是不同的构成。内层18(例如)也可以含有各种添加剂(例如,阻燃剂、增滑剂、抗粘连剂、抗氧化剂、光稳定剂、增粘剂等)。
如上所述,基材层11具有比内层18的熔解峰值温度高的熔解峰值温度。在内层18为多层结构的情况下,内层18的熔解峰值温度是指熔解峰值温度最高的层(例如第一层18a)的熔解峰值温度。基材层11的熔解峰值温度优选为290℃以上,更优选为290~350℃。作为可以用作基材层11且具有上述范围的熔解峰值温度的树脂膜,可以列举出尼龙膜、PET膜、聚酰胺膜、聚苯硫醚膜(PPS膜)等。作为基材层11,可以使用市售的膜,也可以通过涂布(涂布液的涂布和干燥)来形成基材层11。需要说明的是,基材层11可以为单层结构,也可以为多层结构,也可以通过涂布热固性树脂而形成。另外,基材层11(例如)也可以含有各种添加剂(例如,阻燃剂、增滑剂、抗粘连剂、抗氧化剂、光稳定剂、增粘剂等)。
基材层11的熔解峰值温度T11与内层18的熔解峰值温度T18之间的差(T11-T18)优选为20℃以上,更优选为40~100℃。通过使该温度差为20℃以上,能够更充分地抑制因热封而导致的封装材料20的外观变差。基材层11的厚度优选为5~50μm,更优选为12~30μm。
接下来,对第一粘接层12a、第一防腐蚀处理层13a、阻隔层(金属箔层)15、第二防腐蚀处理层13b、以及第二粘接层12b进行说明。这些层具有与上述内层18和基材层11相同或超过它们的耐热性。
粘接层12a、12b只要具有充分的耐热性即可,例如,可以适当地选择使用一般的干式层压用粘接剂、酸改性的热熔接性树脂、热固性粘接剂等公知的粘接剂。作为热固性粘接剂,例如可以列举出聚酯氨基甲酸酯类粘接剂、环氧类粘接剂。从耐热性的观点来看,粘接层12a、12b都优选由热固性粘接剂的固化产物构成。
阻隔层15是具有导电性的金属层。作为阻隔层15的材料,例如可以列举出铝和不锈钢等,但是从成本和重量(密度)等观点来看,优选铝。防腐蚀处理层13a、13b为用于保护阻隔层15的层。作为防腐蚀处理层13a、13b的一个例子,可以列举出含有稀土类元素氧化物(例如氧化铈)以及磷酸或磷酸盐的层。需要说明的是,如图2所示,从性能上来说优选在阻隔层15的两面形成防腐蚀处理层13a、13b,但是考虑到成本方面,也可以只配置防腐蚀处理层13b。
(金属端子)
图4是图1所示的端子用树脂膜和金属端子的IV-IV线方向的剖面图。在一对(在图1的情况下,为2个)金属端子30、30中,一个金属端子30与蓄电装置主体10的正极电连接,另一个金属端子30与蓄电装置主体10的负极电连接。一对金属端子30、30从蓄电装置主体10延伸到封装材料20的外部。一对金属端子30、30的形状例如可以是平板状。
金属端子30的材料可以使用金属。作为金属端子30的材料的金属,可以通过考虑蓄电装置主体10的结构和蓄电装置主体10的各构成要素的材料等来决定。例如,在蓄电装置100为全固态电池的情况下,优选使用铝作为与蓄电装置主体10的正极连接的金属端子30的材料。优选使用表面形成有镀镍层的铜或镍作为与蓄电装置主体10的负极连接的金属端子30的材料。
金属端子30的厚度取决于全固态电池的尺寸和容量。在全固态电池是小型的情况下,金属端子30的厚度例如可以设为50μm以上。另外,在蓄电、车载用等大型全固态电池的情况下,金属端子30的厚度例如可以在100~500μm的范围内适当地设定。
(端子用树脂膜)
如图4所示,端子用树脂膜40以覆盖金属端子30的一部分外周面的方式而配置。通过将端子用树脂膜40配置在金属端子30与封装材料20之间,能够更高地实现蓄电装置100的密封性和绝缘性。端子用树脂膜40具有与上述内层18和基材层11相同或超过它们的耐热性。需要说明的是,在通过封装材料20的内层18就能够充分地确保蓄电装置100的密封性和绝缘性的情况下,也可以不使用端子用树脂膜40。
端子用树脂膜40由对金属端子30具有密合性的树脂组合物构成,优选的是,该树脂组合物包括热固性树脂和熔解峰值温度为160℃以上的热塑性树脂中的至少一者,并且不包括熔解峰值温度小于160℃的热塑性树脂。根据这样构成的端子用树脂膜40,即使在例如100~150℃的温度条件下使用蓄电装置,并且金属端子30的温度达到例如100~150℃,也能够充分地保持蓄电装置100的密封性。该树脂组合物也可以包括热固性树脂和熔解峰值温度(熔点)为200℃以上的热塑性树脂中的至少一者,并且不包括熔解峰值温度小于200℃的热塑性树脂。
作为端子用树脂膜40所采用的热固性树脂,可以列举出选自由聚酰亚胺树脂、酚醛树脂、尿素树脂、三聚氰胺树脂、不饱和聚酯树脂、氨基甲酸酯树脂、丙烯酸树脂、环氧树脂、呋喃树脂以及有机硅树脂构成的组中的至少一种树脂。这些热固性树脂对构成金属端子30的表面的金属材料(例如,铝和镍)具有优异的密合性,并且具有优异的耐热性。
作为端子用树脂膜40所采用的热塑性树脂,只要是采用选自由PET、上述PET系树脂、尼龙、聚乙烯醇树脂、聚偏氯乙烯、聚酰胺树脂、聚对苯二甲酸丁二醇酯树脂、聚苯硫醚、聚醚酰亚胺、聚砜、氟树脂、聚酰胺酰亚胺以及醋酸纤维素构成的组中的至少一种树脂即可。这些热塑性树脂对构成金属端子30的表面的金属材料(例如铝和镍)具有优异的密合性,并且具有优异的耐热性。
端子用树脂膜40可以为单层结构,也可以为多层结构。在端子用树脂膜40为单层结构的情况下(参照图5(a)),构成端子用树脂膜40的树脂组合物优选为选自由PET、聚苯硫醚、氨基甲酸酯树脂及环氧树脂构成的组中的一种热塑性树脂和/或选自由氨基甲酸酯树脂及环氧树脂构成的组中的一种热固性树脂。通过将由这些树脂构成的膜用作端子用树脂膜40,易于同时实现对金属端子30的密合性(在热封时树脂组合物在一定程度上流动)和金属端子30的绝缘性(在热封时树脂组合物不会过度流动)的效果。
在端子用树脂膜40为多层结构的情况下,端子用树脂膜40可以被构成为:具备由熔解峰值温度为160~270℃的PET和/或PET系树脂或者熔解峰值温度为260~300℃的聚苯硫醚(PPS)构成的第一层40a;以及形成在第一层40a的与金属端子30相对的一侧的表面上、且由热固性树脂或者熔解峰值温度为160~270℃的热塑性树脂构成的第二层40b(参照图5(b))。通过采用熔解峰值温度足够高的PET和/或PET系树脂或者PPS作为构成第一层40a的树脂,第一层40a在热封时不会熔解,因此能够实现金属端子30的优异的绝缘性。构成第一层40a的树脂(PET和/或PET系树脂)的熔解峰值温度可以为210℃以上。构成第二层40b的树脂(PET和/或PET系树脂)的熔解峰值温度可以为200℃以上。第一层40a的熔解峰值温度SA与第二层40b的熔解峰值温度SB之间的差(SA-SB)优选为10℃以上,更优选为20~100℃。通过使该温度差为10℃以上,能够实现金属端子30的优异的绝缘性。
第一层40a的厚度优选为5~500μm,更优选为20~200μm。通过使第一层40a的厚度为5μm以上,易于确保绝缘性,另一方面,通过使其为500μm以下,可以实现低成本化。第二层40b的厚度优选为5~500μm,更优选为20~200μm。通过使第二层40b的厚度为5μm以上,易于确保密封性,另一方面,通过使其为500μm以下,可以实现低成本化。
在端子用树脂膜40是具备第一层和第二层40a、40b的多层结构的情况下,还可以进一步具备在第一层40a的与形成有第二层40b一侧相反的那一侧的表面上所形成的第三层40c(参照图5(c))。第三层40c可以由热固性树脂或者熔解峰值温度为160~270℃的热塑性树脂构成。
在第一层40a由热固性树脂构成的情况下,第二层40b优选采用流动性比构成第一层40a的热固性树脂高的热固性树脂。根据这样的构成,在热封时可以通过第二层40b而实现对金属端子30的优异的密合性。此外,第三层40c也可以采用流动性比构成第一层40a的热固性树脂高的热固性树脂。根据这样的构成,可以得到密封性更优异的蓄电装置100。
第三层40c的厚度优选为5~500μm,更优选为20~200μm。通过使第三层40c的厚度为5μm以上,易于确保密封性,另一方面,通过使其为500μm以下,可以实现低成本化。
以上,对本发明的实施方式进行了详述,但本发明不限于上述实施方式。例如,在上述实施方式中,示例了将封装材料20应用于作为蓄电装置的全固态电池,但是也可以将封装材料20应用于其他蓄电装置(例如,锂离子电池)。
实施例
以下,基于实施例对本发明进行更具体地说明,但本发明不限于以下实施例。
<封装材料的制作>
(实施例1)
准备了熔解峰值温度为300℃的高耐热聚酰胺膜(厚度:25μm)作为基材层。准备了铝箔(厚度:40μm)作为金属箔层。准备了熔解峰值温度为255℃的PET膜(厚度:75μm、单层结构)作为内层。通过使用热固性粘接剂(聚酯氨基甲酸酯类)将基材层与金属箔层粘接,并且使用与此相同的粘接剂将金属箔层与内层粘接,从而得到了本实施例涉及的封装材料。
(实施例2)
除了使用熔解峰值温度为290℃的PPS膜(厚度:100μm)以替代高耐热聚酰胺膜来作为基材层以外,与实施例1同样地得到了本实施例涉及的封装材料。
(实施例3)
除了使用环氧类的热固性粘接剂以替代使用聚酯氨基甲酸酯类的热固性粘接剂以外,与实施例1同样地得到了本实施例涉及的封装材料。
(实施例4)
除了使用聚丙烯类粘接剂(熔解峰值温度:85℃)以替代使用聚酯氨基甲酸酯类的热固性粘接剂以外,与实施例1同样地得到了本实施例涉及的封装材料。
(比较例1)
准备了熔解峰值温度为225℃的尼龙膜(厚度:25μm)作为基材层。准备了铝箔(厚度:40μm)作为金属箔层。准备了熔解峰值温度为140℃的聚丙烯膜(厚度:75μm、单层结构)作为内层。通过使用聚丙烯类粘接剂(熔解峰值温度:85℃)将基材层与金属箔层粘接,并且使用与此相同的粘接剂将金属箔层与内层粘接,从而得到了本比较例涉及的封装材料。
(比较例2)
除了使用熔解峰值温度为255℃的PET膜(厚度:25μm)以替代高耐热聚酰胺膜来作为基材层以外,与实施例1同样地得到了本比较例涉及的封装材料。
<密封强度的评价>
将各例中所制作的封装材料以60mm×80mm的尺寸切成2片,并将短边彼此重合,在280℃、表面压力0.5MPa、时间10秒钟的条件下对短边进行热封。将热封部分切成15mm的宽度,从而得到了测定样品。在以下条件下测定了各样品在高温条件下的密封强度。
测定装置:INSTRON公司制造的万能材料试验机
测定温度:150℃
测定时间:将样品在150℃的温度条件下投入后经过5秒钟后开始进行测定。
测定方法:根据JIS K6854-2:1990“粘接剂-剥离粘接强度试验-第2部分:180度剥离”中所记载的方法(剥离方法:T字、剥离速度50mm/分钟),测定了剥离强度(热封强度)。评价按以下标准进行。结果如表1和表2所示。
“A”:剥离强度为10N/15mm以上
“B”:剥离强度小于10N/15mm
<外观评价>
通过目视确认评价密封强度后的样品的热封部,进行了外观的评价。评价按以下标准进行,评价C不优选。结果如表1所示。
“A”:刚密封后没有发现基材层的外观熔解,也没有发现变色。
“B”:刚密封后虽然没有发现基材层的外观熔解,但是发现有变色。
“C”:刚密封后发现基材层的外观熔解。
[表1]
[表2]
工业实用性
根据本发明,提供了用于制造具有优异外观的蓄电装置且耐热性优异的封装材料、以及使用了该封装材料的蓄电装置。
符号说明
10···蓄电装置主体;11···基材层;12a···第一粘接层;15···阻隔层(金属箔层);12b···第二粘接层;18···内层;18a···第一层;18b···第二层;18c···第三层;20···封装材料;30···金属端子(电流输出端子);40···端子用树脂膜;100···蓄电装置。
Claims (14)
1.一种封装材料,为蓄电装置用封装材料,具有层叠结构,该层叠结构依次具备:
基材层、
第一粘接层、
金属箔层、
第二粘接层、以及
含有聚酯系树脂的内层,
所述内层在160~280℃的范围内具有利用差示扫描量热仪所测定的熔解时的熔解峰值温度,
所述基材层具有比所述内层的熔解峰值温度高的熔解峰值温度。
2.根据权利要求1所述的封装材料,其用于全固态电池。
3.根据权利要求1或权利要求2所述的封装材料,其中,所述内层为单层结构。
4.根据权利要求1或权利要求2所述的封装材料,其中,所述内层具有多层结构,该多层结构具备:
含有聚酯系树脂且熔解峰值温度为170~280℃的第一层、以及
形成在所述第一层的内侧的表面上且含有热固性树脂的第二层。
5.根据权利要求1或权利要求2所述的封装材料,其中,所述内层具有多层结构,该多层结构具备:
含有聚酯系树脂且熔解峰值温度为170~280℃的第一层、以及
形成在所述第一层的内侧的表面上且含有聚酯系树脂的第二层,
所述第二层的熔解峰值温度在160~270℃的范围内并且比所述第一层的熔解峰值温度低。
6.根据权利要求5所述的封装材料,其中,所述第一层的熔点TA与所述第二层的熔点TB之间的差TA-TB为10℃以上。
7.根据权利要求4至权利要求6中任意一项所述的封装材料,其进一步具备在所述第一层的与形成有所述第二层的一侧相反的那一侧的表面上所形成的第三层,
所述第三层含有聚酯系树脂,并且熔解峰值温度在160~270℃的范围内且比所述第一层的熔解峰值温度低。
8.根据权利要求4至权利要求6中任意一项所述的封装材料,其进一步具备在所述第一层的与形成有所述第二层的一侧相反的那一侧的表面上所形成的第三层,
所述第三层含有热固性树脂。
9.根据权利要求1至权利要求8中任意一项所述的封装材料,其中,所述聚酯系树脂为聚对苯二甲酸乙二醇酯以及聚对苯二甲酸乙二醇酯系树脂中的至少一者。
10.根据权利要求9所述的封装材料,其中,所述聚对苯二甲酸乙二醇酯系树脂包含源自乙二醇的结构单元、源自对苯二甲酸的结构单元、以及其他结构单元,
成为所述其他结构单元的来源的二元醇成分为选自由新戊二醇、1,4-丁二醇及二乙二醇构成的组中的至少一种。
11.根据权利要求9或权利要求10所述的封装材料,其中,所述聚对苯二甲酸乙二醇酯系树脂包含源自乙二醇的结构单元、源自对苯二甲酸的结构单元、以及其他结构单元,
成为所述其他结构单元的来源的酸成分为选自由间苯二甲酸、己二酸及癸二酸构成的组中的至少一种。
12.根据权利要求1至权利要求11中任意一项所述的封装材料,其中,所述第一粘接层和所述第二粘接层由热固性粘接剂的固化产物构成。
13.一种蓄电装置,具备:
蓄电装置主体、
从所述蓄电装置主体延伸出来的电流输出端子、以及
夹持着所述电流输出端子且容纳所述蓄电装置主体的权利要求1至权利要求12中任意一项所述的封装材料。
14.根据权利要求13所述的蓄电装置,其为全固态电池。
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KR102626933B1 (ko) * | 2021-06-10 | 2024-01-22 | 율촌화학 주식회사 | 계면 박리 조절을 통해 가스배출이 용이한 셀 파우치용 실란트 필름, 이를 포함하는 셀 파우치 및 그 제조 방법 |
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