CN111653694B - 一种电池装置用外包装材料及电池 - Google Patents
一种电池装置用外包装材料及电池 Download PDFInfo
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- CN111653694B CN111653694B CN202010434841.9A CN202010434841A CN111653694B CN 111653694 B CN111653694 B CN 111653694B CN 202010434841 A CN202010434841 A CN 202010434841A CN 111653694 B CN111653694 B CN 111653694B
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Images
Classifications
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- C22C21/08—Alloys based on aluminium with magnesium as the next major constituent with silicon
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
- H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
- H01M50/129—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers with two or more layers of only organic material
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- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
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- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明公开了一种电池装置用外包装材料,包括基材层、粘结层、阻隔层、另一粘结层、热熔接层;所述粘结层设置在所述基材层和所述阻隔层之间;所述另一粘结层设置在所述阻隔层和所述热熔接层之间;所述阻隔层是由铝合金箔组成,所述铝合金箔是由单层或多层构成;所述铝合金箔其成分及其质量百分比包括Fe含量在1.2%以上,Mg含量在1%以上;经过退火处理后,Mg会大量从铝箔内析出,析出Mg量与析出AL量的比值在2‑4之间。通过添加1%‑2%的Mg,提高铝塑复合膜的耐电解液性,通过降低铝箔中Si含量和添加Sb含量,可以细化铝箔内部结晶,加深成型极限深度,从而解决现有铝塑膜冲深及耐电解液腐蚀性能差的问题。
Description
技术领域
本发明涉及铝塑膜生产技术领域,尤其涉及一种电池装置用外包装材料及电池。
背景技术
目前锂离子电池主要分为方形、圆柱、软包三大类,其中方形和圆柱的外壳主要采用铝合金、不锈钢等硬壳,铝合金外壳可为纯铝,而软包的外壳则采用铝塑复合膜膜,极大地改善了硬装电池外形设计不灵活的问题。
铝塑复合膜的从外到内的构成依次是表层尼龙,外层胶水,铝箔,内层胶水和热封层。作为电池外包材料,要求铝塑膜具备高冲深和耐电解液腐蚀的性能,从而防止发生漏液等问题,保证电池使用寿命。
用于锂离子电池外包装用的铝塑复合膜中铝箔材料一般为热处理的8021或者8079系合金材料,厚度从20μm-100μm。锂离子电池用硬壳罐材一般使用未经热处理的3003或者3004系铝箔,厚度在100μm以上。
不同系列的铝箔材料,含有不同合金成分,使用用途也不同。8021材的AL合金成分比如下表所示:
表1 A8021材合金成分比
从上表可以看出现有的8021材合金特征是含有1.2%~1.7%的Fe,其次是含有0.15%以下的Si。由于铝土原料本身就是多种合金的混合物,与其说为了改善材料特性而添加Si,不如说是原料中必定会混入Si成分。但是如果在生产过程中对Si含量不进行管理控制的话,会影响铝箔的品质稳定性,所以Si的目标含有量通常控制在0.2%以下。
影响铝箔冲深性能的三个因素是拉伸强度、0.2%屈服点、及拉伸率。其中拉伸强度和拉伸率等机械性质与合金成分中Fe的析出状态有很大的关系。而Fe析出状态的影响因素之一就是铝箔中Si的含有量。在铝箔生产工序中,Si具有促进Fe析出的效果,进而与Fe、Al形成一种中间化合物,在退火时起到作为再结晶核的作用。虽然结晶核的起点粒径大小多为φ1μm左右,但最终形成的结晶粒径很小。
铝塑复合膜中使用热处理的8021或者8079系合金铝箔的原因之一是因为其含有一定量的Fe成分,伸缩性比其他铝箔大,有利于铝塑复合膜的冲深成型。在锂离子电池中,铝塑复合膜需要通过热封的方式把正、负极极耳、集流体、电解液等封装起来。电解液是由电解质LiPF6和EC/DEC/DMC等作为溶剂组成。
由于热封不良、正负极极耳毛刺等原因,电解液会渗透到铝塑复合膜中,电解质中的锂离子会与铝塑复合膜中铝箔接触。同时,如果负极耳的毛刺部分与铝塑复合膜中铝箔接触,就会引起短路。铝塑复合膜中与电解质锂离子接触的铝箔就会发生腐蚀现象,形成Li-AL合金。由于Li-AL合金非常坚固,只要较小的冲击力度,就会发生锂离子电池外包装铝塑复合膜的穿破。如果发生这种情况,密封的电解液会从该贯通的孔中漏出,再溶解周边,这就是所谓的腐蚀漏液,会严重影响锂离子电池的安全性能。
另外,锂离子电池用硬壳罐材是以未热处理的3003或3004系铝合金,由于其Mn元素的含量在1%-1.5%,故其刚性高,与热处理的8021系或8079系铝合金相比,冲深成型性较差,将其压延成20μm-100μm的厚度,3004系铝合金仍不能进行冲深成型,但据已知含有Mg合金的未热处理3004系铝合金与含锂电解液不容易形成Li合金。另外,Mg含量在2.2-5%、Fe含量在0.4%的5052系铝合金也不容易形成Li合金广为人知,但因其Zn含量0.1%、Cr含量0.15-0.35%,所以刚性非常高,很难单独制作成20μm-100μm的箔材,而且即使能成箔,成型性也要比3004系铝箔差,所以不能用到铝塑复合膜中。
发明内容
有鉴于此,本发明期望提供一种电池装置用外包装材料及电池,解决现有铝塑膜冲深及耐电解液腐蚀性能差的问题。
为达到上述目的,本发明的技术方案是这样实现的:
本发明提供一种电池装置用外包装材料,包括基材层、粘结层、阻隔层、另一粘结层、热熔接层;所述粘结层设置在所述基材层和所述阻隔层之间;所述另一粘结层设置在所述阻隔层和所述热熔接层之间;所述阻隔层是由铝合金箔组成,所述铝合金箔是由单层或多层构成;所述铝合金箔其成分及其质量百分比包括Fe含量在1.2%以上,Mg含量在1%以上;经过退火处理后,Mg会大量从铝箔内析出,析出Mg量与析出AL量的比值在2-4之间。
进一步地,所述铝合金箔其成分还包括Si含量为0.01%-0.2%,Sb含量为0.02%-0.06%,Mn含量在0.01%以下,Zn含量在0.03%以下,Cr含量在0.01%以下。
进一步地,所述铝合金箔其成分中Mg含量为1%-2%。
进一步地,所述铝合金箔其成分中Fe含量为1.2%-2%。
进一步地,所述铝合金箔的晶粒直径的平均值为10μm以下。
优选的,所述铝合金箔的晶粒直径的平均值为5μm以下。
进一步地,所述铝合金箔中占全体90%以上的晶粒尺寸分布在直径0.01-30μm。
优选的,所述铝合金箔中占全体90%以上的晶粒尺寸分布在直径0.01-25μm。
更进一步地,比晶粒直径的平均值小的晶粒直径为整体的70%以上。
进一步地,所述铝合金箔的厚度在20-100μm之间。
进一步地,至少与热熔接层复合的阻隔层表面经过耐腐蚀处理,耐腐蚀剂成分包括氨基苯酚、聚丙烯酸和改性聚烯烃,处理方式包括硝酸铬盐处理、磷酸铬盐处理和铈处理,耐腐蚀层的厚度在2μm以下。
进一步地,所述热熔接层由单层或多层的改性聚丙烯、聚丙烯或聚烯烃组成,厚度在20-120μm。
本发明还提供了一种电池,其特征在于:使用如权利要求1-9中任一种电池装置用外包装材料。
本发明有益效果如下:
1)本发明提供一种电池装置用外包装材料,通过添加1%-2%的Mg,可以有效抑制铝塑复合膜与金属极耳间短路带来的Li-AL合金,提高铝塑复合膜的耐电解液性;
2)本发明提供一种电池装置用外包装材料,通过将不同型号的铝合金采用复合压延的方式制得阻隔层,一方面既提高金属阻隔层的冲深成型性和耐腐蚀性,另一方面又降低了本发明铝箔的使用量,降低了使用成本;
3)本发明提供一种电池装置用外包装材料,通过将铝箔中Si含量降低至0.01%-0.2%,可以细化铝箔内部结晶,加深成型极限深度;
4)本发明通过添加0.02%-0.06%的Sb,可以细化铝箔内部结晶,加深成型极限深度。
附图说明
图1为本发明一些实施方式中电化学装置隔离膜的结构示意图;
其中,1为基材层;2为粘结层;3为着色层;4为耐腐蚀层;5为阻隔层;6为耐腐蚀层;7为另一粘结层;8为热熔接层。
具体实施方式
以下结合附图对本发明的具体实施方式进行详细说明。应当理解的是,此处所描述的具体实施方式仅用于说明和解释本发明,并不用于限制本发明。
本发明具体实施方式提供了一种电池装置用外包装材料,包括基材层1、粘结层2、阻隔层5、另一粘结层7、热熔接层8;所述粘结层2设置在所述基材层1和所述阻隔层5之间;所述另一粘结层7设置在所述阻隔层5和所述热熔接层8之间。下面具体详细的说明本发明一些实施方式中的电池装置用外包装材料的结构。
基材层1:
基材层1的设置以能发挥作为电池用包装材料的基材机能为目的,基材层1位于电池用包装材料的外层侧。关于形成基材层1的原材料,作为基材的机能,以至少具备绝缘性为限度,本发明中没有特别限制。例如可利用树脂制成,树脂中也可添加后述添加剂。
基材层1由树脂制成时,例如可以是由树脂形成树脂膜品,也可是涂布树脂品。作为树脂膜,可以是未延伸膜,也可以是延伸膜。作为延伸膜,可以是一轴延伸膜,也可以是二轴延伸膜,优选二轴延伸膜。作为二轴延伸膜的制成方法,例如逐步二轴延伸法,吹膜法,同步拉伸法。作为树脂涂布法,例如辊涂布法,微凹涂布法,挤出涂布法等。
作为形成基材层1的树脂,例如聚酯、聚酰胺、聚烯烃、环氧树脂、丙烯酸树脂、氟树脂、聚氨酯、硅树脂、酚醛树脂等树脂,或这些树脂的改性物。此外,形成基材层1的树脂可以是这些树脂的共聚物,也可以是共聚物的改性物,亦可以是这些树脂的混合物。
本发明的一些实施方式中,优选聚酯、聚酰胺。
作为聚酯,具体而言,可以举出聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯、聚间苯二甲酸乙二醇酯、共聚聚酯等。另外,作为共聚聚酯,可以举出以对苯二甲酸乙二醇酯为重复单元的主体的共聚聚酯等。具体而言,将对苯二甲酸乙二醇酯作为重复单元的主体而与间苯二甲酸乙二醇酯聚合的共聚物聚酯(以下简称为聚乙烯(对苯二甲酸酯/间苯二甲酸酯))、聚乙烯(对苯二甲酸酯/己二酸酯)、聚乙烯(对苯二甲酸酯/螺母)聚乙烯(对苯二甲酸酯/间苯二甲酸钠)、聚乙烯(对苯二甲酸酯/苯基-二羧酸酯)、聚乙烯(对苯二甲酸酯/癸烷二羧酸酯)等。这些聚酯可以单独使用1种,也可以将2种以上组合使用。
作为聚酰胺,具体而言,可以举出尼龙6、尼龙66、尼龙610、尼龙12、尼龙46、尼龙6与尼龙66共聚物等脂肪族聚酰胺;含有来自对苯二甲酸和/或间苯二甲酸结构单元的尼龙6I、尼龙6T、尼龙6IT、尼龙6I6T(I表示间苯二甲酸,t表示对苯二甲酸)等六亚甲基二胺-间苯二甲酸-对苯二甲酸共聚聚酰胺、聚酰胺MXD6(聚酰胺PACM6(聚双(4-氨基环己基)甲烷叠氮酰胺)等脂环式聚酰胺;进而,内酰胺成分、使4,4’-二苯基甲烷-二异氰酸酯等异氰酸酯成分共聚而成的聚酰胺、作为共聚聚酰胺与聚酯或聚亚烷基醚二醇的共聚物的聚酯酰胺共聚物或聚醚酯酰胺共聚物。这些聚酰胺可以单独使用1种,也可以将2种以上组合使用。
本发明的一些实施方式中,基材层1优选含有聚酯膜、聚酰胺膜及聚烯烃膜中的至少一种;优选含有拉伸聚酯膜及拉伸聚酰胺膜及拉伸聚烯烃膜中的至少一种;进一步优选包含拉伸聚对苯二甲酸乙二醇酯膜、拉伸聚对苯二甲酸丁二醇酯膜、拉伸尼龙膜、拉伸聚丙烯膜中至少一种;进一步优选包含双向拉伸聚对苯二甲酸乙二醇酯膜、双向拉伸聚对苯二甲酸丁二醇酯膜、双向拉伸尼龙膜、双向拉伸聚丙烯膜中至少一种。
基材层1可以是单层,也可以由2层以上构成。基材层1由2层以上构成时,基材层1可以是通过粘接剂等层叠树脂膜而成的层叠体,也可以是将树脂共挤出而形成2层以上的树脂膜的层叠体。另外,可以将共挤出树脂而形成2层以上的树脂膜的层叠体在未拉伸的状态下作为基材层1,也可以进行单轴拉伸或双轴拉伸后作为基材层1。
在基材层1中,作为2层以上的树脂膜的层叠体的具体例,可以举出聚酯膜与尼龙膜的层叠体、2层以上的尼龙膜的层叠体、2层以上的聚酯膜的层叠体等,优选拉伸尼龙膜与拉伸聚酯膜层叠体、2层以上的拉伸尼龙膜的层叠体、2层以上的拉伸聚酯膜的层叠体。例如,在基材层1为2层树脂膜的层叠体的情况下,优选聚酯树脂膜和聚酯树脂膜的层叠体、聚酰胺树脂膜和聚酰胺树脂膜的层叠体、或者聚酯树脂膜和聚酰胺树脂膜的层叠体,更优选聚对苯二甲酸乙二醇酯膜和聚对苯二甲酸乙二醇酯膜的层叠体、尼龙膜和尼龙膜的层叠体、或者聚对苯二甲酸乙二醇酯膜和尼龙膜的层叠体。另外,聚酯树脂在例如电解液附着于表面时难以变色,因此在基材层1为两层以上的树脂膜的层叠体的情况下,优选聚酯树脂膜位于基材层的最外层。
当基材层1为两层以上的树脂膜的层叠体时,两层以上的树脂膜也可以通过粘接剂层叠。作为优选的粘接剂,可举出与后述粘接剂层2例示的粘接剂相同的粘接剂。另外,作为层叠两层以上的树脂膜的方法,没有特别限制,可以采用公知方法,例如可以举出干式层叠法、夹层层叠法、挤出层叠法、热层叠法等,优选干式层叠法。通过干式层叠法进行层压时,作为粘接剂优选使用聚氨酯粘接剂。此时,粘合剂的厚度例如可以是大约2-5μm。此外,可以在树脂薄膜上形成锚固涂层并层叠。锚固涂层可举出与后述粘接剂层2中例示的粘接剂相同的物质。此时,锚固涂层的厚度例如可举出0.01-1.0μm左右。
此外,基材层1的表面和内部中的至少一个可以存在润滑剂、阻燃剂、防粘连剂、抗氧化剂、光稳定剂、增粘剂、抗静电剂等添加剂。添加剂可以只使用一种,也可以混合使用两种以上。
从提高电池用包装材料的成形性的观点出发,优选在基材层的表面形成润滑剂。作为润滑剂,本发明没有特别限制,优选可举出酰胺系润滑剂。酰胺类润滑剂的具体例子包括饱和脂肪酸酰胺、不饱和脂肪酸酰胺、取代酰胺、羟甲基酰胺、饱和脂肪酸双酰胺、不饱和脂肪酸双酰胺、脂肪酸酯酰胺和芳香族双酰胺。作为饱和脂肪酸酰胺的具体例子,可以举出月桂酸酰胺、棕榈酸酰胺、硬脂酸酰胺、山嵛酸酰胺、羟基硬脂酸酰胺等。作为不饱和脂肪酸酰胺的具体例子,可以举出油酸酰胺、芥酸酰胺等。取代酰胺的具体例子包括N-油棕榈酸酰胺、N-硬脂酰胺、N-硬脂酰胺、N-油硬脂酰胺和N-硬脂酰胺。另外,作为羟甲基酰胺的具体例子,可以举出羟甲基硬脂酸酰胺等。饱和脂肪酸双酰胺具体实例包括亚甲基双硬脂酸酰胺、亚乙基双辛酸酰胺、亚乙基双月桂酸酰胺、亚乙基双硬脂酸酰胺、亚乙基双羟基硬脂酸酰胺、亚乙基双山嵛酸酰胺和六亚甲基双硬脂酸六亚甲基双山嵛酸酰胺、六亚甲基羟基硬脂酸酰胺、n,n’-二硬脂基己二酸酰胺、n,n’-二硬脂基癸二酸酰胺等。不饱和脂肪酸双酰胺的具体例子包括乙烯双油酸酰胺、乙烯双芥酸酰胺、六亚甲基双油酸酰胺、n,n’-二油基己二酸酰胺和n,n’-二油基癸二酸酰胺。作为脂肪酸酯酰胺的具体例子,可以举出硬脂酰胺乙基硬脂酸酯等。另外,作为芳香族双酰胺的具体例子,可以举出间苯二甲基双硬脂酸酰胺、间苯二甲基双羟基硬脂酸酰胺、n,n’-二硬脂基间苯二甲酸酰胺等。润滑剂可以单独使用1种,也可以将两种以上组合使用。
基材层1的表面存在润滑剂时,关于涂布量,本发明没有特别限制,优选列举出约3mg/m2以上,更优选列举出4-30mg/m2左右。存在于基材层表面的润滑剂可以是使构成基材层的树脂中含有的润滑剂渗出的润滑剂,也可以是在基材层的表面涂布的润滑剂。
关于基材层的厚度,只要发挥作为基材的功能即可,本发明没有特别限制,例如可列举出3-50μm左右、优选10-35μm左右。基材层为2层以上的树脂膜的层叠体时,作为构成各层的树脂膜的厚度,分别优选举出2-30μm左右。
粘结层2:
粘结层2是以提高基材层1与阻隔层5之间的粘接性为目的,根据需要在它们之间设置的层。
粘结层2由能够粘接基材层1和阻隔层5的粘接剂形成。用于形成粘结层2的粘接剂本发明中没有限定,例如可以是双组分固化型粘接剂(双组分粘接剂),另外,也可以是单组分固化型粘接剂(单组分粘接剂)。并且,形成粘结层2时使用的粘接剂可以是化学反应型、溶剂挥发型、热熔融型、热压型等中的任一种。另外,粘结层2可以是单层,也可以是多层。
作为粘接剂中所含的粘接成分,具体而言,可以举出聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯、聚间苯二甲酸乙二醇酯、共聚聚酯等聚酯;聚醚;聚氨酯;环氧树脂;酚醛树脂;尼龙6、尼龙66、尼龙12、共聚聚酰胺等聚酰胺;聚烯烃、环状聚烯烃、酸改性聚烯烃、酸改性环状聚烯烃等聚烯烃系树脂;聚乙酸乙烯酯;纤维素;(甲基)丙烯酸树脂;聚酰亚胺;聚碳酸酯;尿素树脂、三聚氰胺树脂等氨基树脂;氯丁橡胶、丁腈橡胶、苯乙烯-丁二烯橡胶等橡胶;有机硅树脂等。这些粘接成分可以单独使用1种,也可以将2种以上组合使用。在这些粘接成分中,优选聚氨酯粘接剂。
作为聚氨酯粘接剂,例如可以举出包含含有多元醇化合物的主剂和含有异氰酸酯化合物的固化剂的聚氨酯粘接剂。
另外,粘结层2只要不妨碍粘接性,就允许添加其他成分,可以含有着色剂、热塑性弹性体、增粘剂、填料等。通过粘结层2含有着色剂,可以对电池用包装材料进行着色。作为着色剂,可以使用颜料、染料等公知着色剂。另外,着色剂可以仅使用1种,也可以混合两种以上使用。
颜料的种类只要是不损害粘结层2的粘接性的范围,就没有特别限定。作为有机颜料,例如可以举出偶氮系、酞菁系、喹吖啶酮系、蒽醌系、二恶嗪系、靛硫靛系、苝系、异吲哚啉系等颜料,作为无机颜料,可以举出炭黑系、氧化钛系、镉系、铅系、异吲哚啉系等颜料。在着色剂中,例如为了使电池用包装材料的外观成为黑色,优选炭黑。
作为颜料的平均粒径,没有特别限制,例如可以举出0.05-5μm左右、优选0.08-2μm左右。另外,颜料的平均粒径为由激光衍射/散射式粒径分布测定装置测定的中值粒径。
作为粘结层2中的颜料的含量,只要电池用包装材料被着色就没有特别限制,例如可举出5-60%左右、优选10-40%。
粘结层2的厚度只要能够粘接基材层1和阻隔层3即可,没有特别限制,作为下限,例如可列举出约1μm以上或约2μm以上,作为上限,可列举出约10μm以下或约5μm以下,作为优选的范围,可列举出1-10μm左右、1-5μm左右。
着色层3:
在本发明的一些实施方式中,还包括着色层3。
着色层3是根据需要设置在基材层1和阻隔层5之间的层。在具有粘结层2的情况下,也可以在基材层1与粘结层2之间、粘结层2与阻隔层5之间设置着色层。另外,也可以在基材层1的外侧设置着色层3。通过设置着色层3,可以对电池用包装材料进行着色。
着色层3例如可以通过将含有着色剂的油墨涂布在基材层1的表面、粘结层2的表面或者阻隔层5的表面而形成。作为着色剂,可以使用颜料、染料等公知着色剂。另外,着色剂可以仅使用1种,也可以混合2种以上使用。
作为着色层3中含有的着色剂的具体例子,可以与粘结层2中例示的着色剂相同的着色剂。
阻隔层5:
在电池用外包装材料中,阻隔层5是至少能够抑制水分浸入的层。
本发明的一些实施方式中所述阻隔层5是由铝合金箔组成,所述铝合金箔是由单层或多层构成;所述铝合金箔其成分及其质量百分比包括Fe含量在1.2%以上,Mg含量在1%以上;经过退火处理后,Mg会大量从铝箔内析出,析出Mg量与析出AL量的比值在2-4之间。
具体地,所述铝合金箔其成分还包括Si含量为0.01%-0.2%,Sb含量为0.02%-0.06%,Mn含量在0.01%以下,Zn含量在0.03%以下,Cr含量在0.01%以下。
具体地,所述铝合金箔其成分中Mg含量为1%-2%。
具体地,所述铝合金箔其成分中Fe含量为1.2%-2%。
具体地,所述铝合金箔的晶粒直径的平均值为10μm以下。
优选的,所述铝合金箔的晶粒直径的平均值为5μm以下。
具体地,所述铝合金箔中占全体90%以上的晶粒尺寸分布在直径0.01-30μm。
优选的,所述铝合金箔中占全体90%以上的晶粒尺寸分布在直径0.01-25μm。
更具体地,比晶粒直径的平均值小的晶粒直径为整体的70%以上。
具体地,所述铝合金箔的厚度在20-100μm之间。
本发明的一些实施方式中铝合金箔可以为2层以上的复合层,复合层可以在真空中进行压延,也可以在一般环境中进行压延,通常在压延到所需厚度前不进行特殊处理。
耐腐蚀层6:
在阻隔层5为金属箔的情况下,为了防止溶解或腐蚀等问题,优选至少在与基材层1侧相反的另一侧面上附着耐腐蚀性皮膜。可以选择在阻隔层5的两侧附着耐腐蚀性皮膜。所述耐腐蚀性皮膜是指,例如在阻隔层5的表面进行勃姆石处理等水热处理、化合处理、阳极氧化处理、镍或铬等电镀处理、涂布形成涂层的防腐蚀处理,使阻隔层5具备耐腐蚀性的薄膜。作为形成耐腐蚀性皮膜的处理,可以进行1种,也可以将2种以上组合进行。处理膜不仅只限于一层,也可以多层化组合。在这些处理中,水热处理及阳极氧化处理是利用处理剂使金属箔表面溶解,形成耐腐蚀性优异的金属化合物的处理。另外,这些处理有时也被包含在化合处理的定义中。在一般阻隔层具备耐腐蚀性皮膜的情况下,包括耐腐蚀性皮膜在内作为一同作为阻隔层5。
耐腐蚀性皮膜在电池用包装材料成型时,通过阻止阻隔层5(例如铝合金箔)与基材层1间的分层、避免电解质与水分的反应生成的氟化氢,从而防止阻隔层5表面的溶解、腐蚀,特别是防止在阻隔层5为铝合金箔的情况下存在于其表面的氧化铝溶解与腐蚀,同时提高阻隔层5表面的粘接性(润湿性),具有防止热封及成型时基材层1和阻隔层5间分层的效果。
作为通过化合处理形成的耐腐蚀性皮膜,已知有许多种类,此处将主要列举含有磷酸盐、铬酸盐、氟化物、三嗪硫醇化合物以及稀土类氧化物等成分中至少一种的耐腐蚀性皮膜。
作为使用了磷酸盐、铬酸盐的化合处理,主要包括例如铬酸镀铬处理、磷酸镀铬处理、磷酸-铬酸盐处理、铬酸盐处理等,作为在这些处理中使用的铬化合物,主要包括例如硝酸铬、氟化铬、硫酸铬、醋酸铬、草酸铬、重磷酸铬、乙酰乙酸铬酸酯、氯化铬、硫酸钾铬等。作为用于这些处理的磷化合物,主要包括例如磷酸钠、磷酸钾、磷酸铵、多磷酸等。作为铬酸盐处理方式,主要包括蚀刻铬酸盐处理、电解铬酸盐处理、涂布型铬酸盐处理等,优选涂布型铬酸盐处理。在该涂布型铬酸盐处理中,首先,利用碱浸渍法、电解清洗法、酸清洗法、电解酸清洗法、氧活化法等普适处理方法对阻隔层5(例如铝合金箔)的至少内侧进行脱脂处理。然后,在脱脂处理面上使用磷酸Cr(铬)盐、磷酸Ti(钛)盐、磷酸Zr(锆)盐、磷酸Zn(锌)盐等磷酸金属盐及以这些金属盐的混合物为主要成分的处理液,或者以磷酸非金属盐及这些非金属盐的混合体为主要成分的处理液、以及含有上述材料与合成树脂形成的混合物的处理液,通过辊涂法、凹版印刷法、浸渍法等公知涂布法涂布并进行干燥处理。处理液可以使用例如水、醇类溶剂、烃类溶剂、酮类溶剂、酯类溶剂、醚类溶剂等各种溶剂,优选水。另外,作为其中使用的树脂成分,可以选择苯酚或聚丙烯酸等水溶性高分子等。
作为耐腐蚀性皮膜的一个例子,将在磷酸中分散有氧化铝、氧化钛、氧化铈、氧化锡等金属氧化物或硫酸钡的微粒物质涂布在阻隔层5的表面,通过在150℃以上进行烧结处理而形成的耐腐蚀性皮膜。
作为耐腐蚀性皮膜的其他例子,主要包括含有选自稀土类元素氧化物溶胶、阴离子性聚合物、阳离子性聚合物中的至少一种成分的涂布型防腐蚀处理而形成的薄膜。涂布剂中还可以含有磷酸或磷酸盐、使聚合物交联的交联剂。稀土类元素氧化物溶胶中,在液体分散介质中分散有稀土类元素氧化物的微粒(例如,平均粒径100nm以下的粒子)。作为稀土类元素氧化物,主要包括氧化铈、氧化钇、氧化钕、氧化镧等,从进一步提高密合性的观点出发,优选氧化铈。耐腐蚀性皮膜所含的稀土类元素氧化物可以单独使用1种,也可以组合使用2种以上。作为稀土类元素氧化物溶胶的液体分散介质,例如可以使用水、醇类溶剂、烃类溶剂、酮类溶剂、酯类溶剂、醚类溶剂等各种溶剂,优选水。作为阳离子性聚合物,主要包括聚乙烯亚胺、由聚乙烯亚胺和具有羧酸聚合物构成的离子高分子络合物、在丙烯酸类主链上接枝聚合了伯胺的伯胺接枝丙烯酸类树脂、聚烯丙胺或其衍生物、氨基化酚等。另外,作为阴离子性聚合物,优选以聚(甲基)丙烯酸或其盐、或者(甲基)丙烯酸及其盐为主要成分的共聚物。交联剂优选为选自具有异氰酸酯基、缩水甘油基、羧基、恶唑啉基中的任意官能团的化合物和硅烷偶联剂中的至少1种。所述磷酸或磷酸盐优选为缩合磷酸或缩合磷酸盐。
耐腐蚀性皮膜根据需要,也可以进一步层叠阳离子性聚合物或阴离子性聚合物中的至少一中形成层叠结构。作为阳离子性聚合物、阴离子性聚合物,主要包含前述聚合物。
作为耐腐蚀性皮膜的厚度,虽然没有特别限制,但从皮膜的凝聚力及与阻隔层5或热熔性树脂层的密合力的角度考虑,优选为1nm-2.0μm,进一步优选为1nm-1μm。
化合处理是通过棒涂法、辊涂法、凹版涂布法、浸渍法等将含有用于形成耐腐蚀性皮膜的化合物的溶液涂布在阻隔层5的表面后,加热至阻隔层5的温度至70-200℃来进行的。另外,也可以在对阻隔层5实施化合处理之前,预先将阻隔层5用于利用碱浸渍法、电解清洗法、酸清洗法、电解酸液清洗法等进行脱脂处理。通过上述脱脂处理,能够更有效地进行阻隔层5表面的化合处理。
粘结层7:
粘结层7是为了使阻隔层5与热熔接层8牢固地粘接而设置的中间层。
粘结层7由能够粘接阻隔层5和热熔接层8的树脂形成。作为用于形成粘结层7的树脂,可使用其粘接机构、粘接剂成分的种类等与粘接剂层2中示例的粘接剂相同的树脂。另外,也可以使用上述热熔接层8中示例的聚烯烃、环状聚烯烃、羧酸改性聚烯烃、羧酸改性环状聚烯烃等聚烯烃系树脂。从提升阻隔层5与热熔接层8的密合性的观点出发,作为聚烯烃,优选羧酸改性聚烯烃,特别优选羧酸改性聚丙烯。即,构成粘结层7的树脂可以含有或不含有聚烯烃主链,优选含聚烯烃主链。构成粘结层7的树脂是否包含聚烯烃主链可以利用例如红外分光法、气相色谱-质谱法等进行分析,对分析方法不作特别限定。
从减薄电池用包装材料的厚度并且提升其成型稳定性的观点出发,粘结层7也可以是含有酸改性聚烯烃和固化剂的树脂组合物的固化物。作为酸改性聚烯烃,优选列举与热熔接层中例示的羧酸改性聚烯烃、羧酸改性环状聚烯烃相同的物质。
作为固化剂,只要是使酸改性聚烯烃固化的固化剂,就没有特别限定。列举例如环氧系固化剂、多官能异氰酸酯系固化剂、碳二亚胺系固化剂、恶唑啉系固化剂等。
作为环氧系固化剂,只要是具有至少1个环氧基的化合物即可,没有特别限定。列举例如双酚A二缩水甘油醚、改性双酚A二缩水甘油醚、酚醛清漆缩水甘油醚、甘油聚缩水甘油醚、聚甘油聚缩水甘油醚等环氧树脂。
作为多官能异氰酸酯系固化剂,只要是分子内具有2个以上异氰酸酯基的化合物,就没有特别限定。列举异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)、甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、及以上物质的聚合或加成后的成分及此类混合物与其他聚合物的反应物。
作为碳化二亚胺系固化剂,只要是分子内具有至少1个碳化二亚胺基(-N=C=N-)的化合物,就没有特别限定。优选具有至少2个以上碳化二亚胺基的聚碳化二亚胺化合物。
作为恶唑啉系固化剂,只要是具有恶唑啉骨架的化合物,就没有特别限定。可以列举日本催化剂公司制造的环氧系列等。
从提高粘结层7与热熔接层8之间的密合性等观点来看,固化剂也可以由两种以上的化合物构成。
对于粘结层7的厚度,只要具备作为粘结层7的功能即可,没有特别限制,但在使用粘结层2中例示的粘接剂的情况下,优选列举1-10μm左右,进一步优选列举1-5μm左右。使用热熔接层8中例示的树脂的情况下,优选列举2-50μm左右,更优选列举出10-40μm左右。如果是酸改性聚烯烃与固化剂的固化物,则优选列举30μm以下,进一步优选列举0.1-20μm左右,更进一步优选列举0.5-5μm左右。需要说明的是,粘结层7为含有酸改性聚烯烃和固化剂的树脂组合物的固化物时,可以通过涂布该树脂组合物并利用加热等使其固化形成粘结层7。
热熔接层8:
热熔接层8为最内层,是在组装电池时发挥热熔接性树脂层彼此热熔接来密封电池元件的功能的层(热封层)。
对于构成热熔接层8的树脂,以可热熔接为限,没有特别限制,优选聚烯烃、酸改性聚烯烃等含有聚烯烃主链的树脂。
作为聚烯烃,具体而言,可以列举低密度聚乙烯、中密度聚乙烯、高密度聚乙烯、线状低密度聚乙烯等聚乙烯乙烯-α-烯烃共聚物;均聚丙烯、聚丙烯嵌段共聚物(例如丙烯与乙烯的嵌段共聚物)、聚丙烯的无规共聚物(例如丙烯与乙烯的无规共聚物)等聚丙烯;丙烯-α-烯烃共聚物;乙烯-丁烯-丙烯的三元共聚物等。其中,优选聚丙烯。作为共聚物时的聚烯烃树脂可以是嵌段共聚物,也可以是无规共聚物。这些聚烯烃系树脂可以单独使用1种,也可以并用2种以上。
酸改性聚烯烃是通过用酸成分与聚烯烃嵌段聚合或接枝聚合而改性的聚合物。作为酸改性的聚烯烃,也可以使用上述聚烯烃、丙烯酸或甲基丙烯酸等极性分子与上述聚烯烃共聚而成的共聚物、或交联聚烯烃等聚合物等。另外,作为酸改性中使用的酸成分,可以列举例如马来酸、丙烯酸、衣康酸、巴豆酸、马来酸酐、衣康酸酐等羧酸或磺酸,以及其酸酐。
热熔接层8可以单独由1种树脂构成,也可以由2种以上的树脂组合而成的共混聚合物构成。并且,热熔接层8可以仅有1层,也可以由2层及以上相同或不同的树脂构成。
热熔接层8根据需要也可以含有爽滑剂等。在热熔接层8含有爽滑剂情况下,能够提高电池用外包装材料的成型性。爽滑剂的类型没有特别限制,可以在公知范围内选择使用。爽滑剂可以单独使用1种,也可以将2种以上组合使用。
作为爽滑剂,没有特别限制,优选可举出酰胺系爽滑剂。可列举出在基材层1示例中的爽滑剂。爽滑剂可以单独使用1种,也可以将2种以上组合使用。
在热熔接层8的表面存在润滑剂的情况下,其含量没有特别限制,但从提高电子包装用材料的成型性的观点出发,优选列举10-50mg/m2,进一步优选列举15-40mg/m2。
存在于热熔接层8表面的爽滑剂可以是从构成热熔接层8的树脂中渗出的爽滑剂,也可以是在热熔接层8的表面涂布的爽滑剂。
对热熔接层8的厚度没有特别限制,只要满足热熔接性树脂层彼此热熔接后的性能并且发挥密封电池元件的功能即可,例如约100μm以下,优选15-85μm左右。
热熔接层8根据需要也可以含有抗氧化剂等成分。含有抗氧化剂的热熔接层8,可以抑制制造工序中的热劣化。抗氧化剂的种类没有特殊限制,可以在公知范围内选择使用。抗氧化剂可以单独使用1种,也可以将2种以上组合使用。
以下将通过实施例对本发明进行详细描述。
在以下实施例和对比例中,性能参数按照如下方法测定:
(1)合金成分组成按照JIS Z 2611的规格,使用发光分光分析法进行测定。
(2)结晶粒径需将电解研磨的资料切片后采用EBSD:电子后向衍射法观察。
(3)铝合金箔的表面Mg、Fe、Al的含有量可通过X射线光电子能谱仪(XPS)进行测定。
(4)拉伸强度
使用拉伸试验装置,把铝塑复合膜制备成直条状,样品尺寸为100*15mm,拉伸速度50mm/min进行测量。
(5)成型深度
成型尺寸80mm×70mm、压制压力0.8MPa、拐角r=1.0mm、凸型边部r角=1.0mm、凸型凹型间隙0.51mm。
(6)耐腐蚀测试
以铝合金为阳极,Li合金为阴极,外接电源充电,充电电压为1V,溶剂为含有1mol/L LiPF6的EC/DEC/DMC锂离子电池用电解液。充电3H后,通过电位差计,检查有无电流产生及目视阳极上是否产生了Li-AL合金来验证铝合金是否发生腐蚀。
实施例1
基材层:
采用厚度为25μm的2段式异步双向拉伸尼龙膜。
铝合金箔层:
采用单层铝合金箔层,厚度为40μm,Mg含量为1%,Fe含量为1.2%,Si含量0.1%,Sb含量0.02%,退火处理后,铝合金表面的Mg与AL的析出比值为2。
对基材层进行电晕处理,在基材层用干铁碾压铝合金箔层。在铝合金箔的暗面涂上双组份聚氨酯粘合剂(多醇化合物和芳香族异氰酸酯类化合物),在铝合金箔上形成粘合剂层2(3μm)。铝合金箔暗面上的粘结层2和基材层1复合后,在60℃的温度下进行3天的熟化处理,形成半成品基材层(25μm)/粘结层(3μm)/铝合金箔层(40μm)。铝合金箔层的两面预先都进行了化学处理。
将重均分子量70000、熔点145℃、酸值为4.5mg KOH/g的无水马来酸酐改性聚丙烯树脂溶解到水溶液中,再加入环氧树脂和甲基磺酸树脂,得到的粘接树脂。将粘结树脂水溶液涂布到半成品铝合金箔层亮面上后进行干燥处理,干燥温度为150℃,形成粘结层7。
作为热熔接层8的内热熔接树脂(CPP)由三层组成,其结构为:
与粘结层7接触的树脂层:由熔点为162℃,MFR(230℃)为5.5g/10min的无规共聚聚丙烯组成的层;
中间树脂层:按重量比,以50%的熔点为162℃,MFR(230℃)为2g/10min的嵌段共聚聚丙烯、20%的熔点为155℃,MFR(230℃)为5g/10min的无规共聚聚丙烯、20%的熔点为160℃,MFR(230℃)为9.5g/10min,密度为0.87g/cm3的丙烯-丁烯组成的聚合物弹性体和10%的MFR(230℃)为3g/10min非结晶性丙烯系弹性体所形成的混合物层;
最内层树脂层:由熔点为145℃,MFR(230℃)为12g/10min的无规共聚聚丙烯组成的层;内热熔接树脂中从与粘结层7接触层到最内层的三层树脂厚度比为3:6:1。
将40μm CPP薄膜表面进行电晕处理,然后将其与粘结层7在160℃温度下热复合后,进一步在160℃的温度下热处理30s。这样就形成了基材层(25μm)/粘结层(3μm)/铝合金箔层(40μm)/粘结层(1.5μm)/热熔接层(40μm)的复合成品。
同时,在基材层表面涂上了Slip剂(爽滑剂)。slip膜层为芥酸酰胺溶液,浓度为10%,一定温度下的干燥处理后,基材层表面芥酸酰胺涂布量为10mg/㎡。
实施例2
基材层:
基材层采用厚度为25μm的2段式异步双向拉伸聚对苯二甲酸丁二醇酯(PBT)膜。
铝合金箔层:
采用单层铝合金箔层,厚度为40μm,Mg含量为1.5%,Fe含量为1.5%,Si含量0.1%,Sb含量0.02%,退火处理后,铝合金表面的Mg与AL的析出比值为3.1。
采用实施例1中方法制备了基材层(25μm)/粘结层(3μm)/铝合金箔层(40μm)/粘结层(1.5μm)/热熔接层(40μm)的复合成品。同时,也在基材层表面涂上了同样量的Slip剂。
实施例3
基材层:
基材层采用厚度为25μm的2段式异步双向拉伸尼龙膜。
铝合金箔层:
采用单层铝合金箔层,厚度为40μm,Mg含量为2%,Fe含量为2%,Si含量0.1%,Sb含量0.02%,退火处理后,铝合金表面的Mg与AL的析出比值为4。
采用实施例1中方法制备了基材层(25μm)/粘结层(3μm)/铝合金箔层(40μm)/粘结层(1.5μm)/热熔接层(40μm)的复合成品。同时,也在基材层表面涂上了同样量的Slip剂。
实施例4
基材层:
基材层采用厚度为25μm的2段式异步双向拉伸聚对苯二甲酸丁二醇酯(PBT)膜。
铝合金箔层:
采用Mg AL合金箔/8021AL箔/Mg AL合金箔的3层复合铝合金箔。中间层的8021AL箔中Fe含量为1.5%,Si含量为0.08%。与基材层1和热熔接层8接触的含Mg AL箔厚度均为10μm,Mg含量为1.5%,Fe含量为1.5%,Si含量0.01%,Sb含量0.04%,退火处理后,铝合金表面的Mg与AL的析出比值为3.1。
对基材层进行电晕处理,在基材层用干铁碾压铝合金箔层。在铝合金箔的一面涂上双组份聚氨酯粘合剂(聚酯多醇化合物和芳香族异氰酸酯类化合物),在铝合金箔上形成粘合剂层2(3μm)。铝合金箔一面上的粘结层2和基材层1复合后,在60℃的温度下进行3天的熟化处理,形成半成品基材层(25μm)/粘结层(3μm)/铝合金箔层(40μm)。铝合金箔层的两面预先都进行了化学处理,形成耐腐蚀层4和6。
粘结层7所用熔融型树脂为无水马来酸酐改性聚丙烯,在铝合金箔的处理面上,形成厚度为20μm的粘结层7,进一步地,与厚度为20μm热熔接树脂复合。粘结层7和热熔接层8通过熔融共挤的方式复合到铝合金箔的另一面上。粘结层7使用的是熔点140℃、MFR(230℃)为5g/10min的无水马来酸酐改性无规共聚聚丙烯60%(按重量比),无水马来酸酐对无规共聚聚丙烯的改性度为10%,熔点160℃、MFR(230℃)为2.6g/10min、密度为0.87g/cm3的丙烯和丁烯的共聚物弹性体24%(按重量比),熔点130℃、MFR(230℃)为9.5g/10min、密度为0.91g/cm3的乙烯和丙烯结晶性共聚物弹性体8%(按重量比)和熔点105℃、MFR(230℃)为12g/10min的低密度聚乙烯8%(按重量比)组成的混合物。
作为热熔接层8的内热熔接树脂由两层组成,其结构为:
与粘结层7接触的树脂层:按重量比,以62%的熔点为155℃,MFR(230℃)为4g/10min的无规共聚聚丙烯、33%的非结晶性的丙烯系弹性体和5%的熔点为110℃,MFR(230℃)为7.5g/10min的低密度聚乙烯所形成的混合物层;
最内层树脂层:由熔点为155℃,MFR(230℃)为15g/10min的无规共聚聚丙烯组成的层;
与粘结层7接触的树脂层与最内层树脂层的厚度比为8:2。
半成品基材层(25μm)/粘结层(3μm)/铝合金箔层(40μm)与粘结层7、热熔接层8复合后,在180℃的温度下进行2s的热处理。
这样就形成了基材层(25μm)/粘结层(3μm)/铝合金箔层(40μm)/粘结层(20μm)/热熔接层(20μm)的复合成品。
同时,在基材层表面涂上了与实施例1同样量的Slip剂。
实施例5
基材层:
基材层采用厚度为25μm的2段式异步双向拉伸聚对苯二甲酸丁二醇酯(PBT)膜。
铝合金箔层:
采用单层铝合金箔层,厚度为100μm,Mg含量为1.5%,Fe含量为1.5%,Si含量0.01%,Sb含量0.04%,退火处理后,铝合金表面的Mg与AL的析出比值为3。
采用实施例1中方法制备了基材层(25μm)/粘结层(3μm)/铝合金箔层(100μm)/粘结层(1.5μm)/热熔接层(40μm)的复合成品。同时,也在基材层表面涂上了同样量的Slip剂。
实施例6
基材层:
基材层使用了厚度为12μm的2段异步双向延伸聚对苯二甲酸乙二醇酯(PET)和厚度为15μm的2段异步延伸尼龙。具体而言,将PET的一面预先进行电晕处理,在电晕处理PET表面涂布双组份聚氨酯粘合剂(多元醇化合物和芳香族异氰酸酯类化合物),形成粘合剂层(3μm)。PET上的粘结层与已进行电晕处理的尼龙复合,形成了PET(12μ)/粘合剂层(3μ)/尼龙层(15μ)的复合基材层。
铝合金箔层:
采用Mg AL合金箔/8079AL箔(厚度比为1:9)的2层复合铝合金箔,复合铝合金箔总厚度为40μm。Mg AL合金箔层中,Mg的含量为1%,Fe含量为1.5%,Si含量0.1%,Sb含量0.02%,退火处理后,铝合金表面的Mg与AL的析出比值为2.1。
将复合基材层中将与铝合金箔中8079AL箔面接触的尼龙膜侧预先进行了电晕处理,然后放置在60℃的温度下熟化处理3天,形成了半成品PET(12μ)/粘合剂层(3μ)/尼龙层(15μ)/粘结层(3μm)/铝合金箔层(40μm)的复合层。
作为热熔接层8的内热熔接树脂由3层组成,其结构为:
与铝合金箔层接触的树脂层:以熔点140℃、MFR(230℃)为5g/10min的无水马来酸酐改性无规共聚聚丙烯60%(按重量比),无水马来酸酐对无规共聚聚丙烯的改性度为10%,熔点160℃、MFR(230℃)为2.6g/10min、密度为0.87g/cm3的丙烯和丁烯的共聚物弹性体24%(按重量比),熔点130℃、MFR(230℃)为9.5g/10min、密度为0.91g/cm3的乙烯和丙烯结晶性共聚物弹性体8%(按重量比)和熔点105℃、MFR(230℃)为12g/10min的低密度聚乙烯8%(按重量比)组成的混合物。
中间树脂层:按重量比,以62%的熔点为155℃,MFR(230℃)为4g/10min的无规共聚聚丙烯、33%的非结晶性的丙烯系弹性体和5%的熔点为110℃,MFR(230℃)为7.5g/10min的低密度聚乙烯所形成的混合物层;
最内层树脂层:由熔点为155℃,MFR(230℃)为15g/10min的无规共聚聚丙烯组成的层;
与铝合金箔层接触的树脂层与中间树脂层与最内层树脂层的厚度比为10:8:2。
作为热熔接层8的内热熔接树脂通过熔融共挤的方式复合到半成品基材层(25μm)/粘结层(3μm)/铝合金箔层(40μm)的Mg AL合金箔面上后,在180℃的温度下进行2s的热处理。
这样就形成了基材层(25μm)/粘结层(3μm)/铝合金箔层(40μm)/热熔接层(40μm)的复合成品。
同时,在基材层表面涂上了与实施例1同样量的Slip剂。
实施例7
基材层:
基材层是由厚度为3μm的2段异步双向拉伸聚对苯二甲酸乙二醇酯(PET)膜、厚度为2μm的酸改性聚烯烃层和厚度为20μm的2段异步双向拉伸尼龙膜组成,总厚度为25μm。
铝合金箔层:
采用Mg AL合金箔/8021AL箔/Mg AL合金箔(厚度比为2:6:2)的3层复合铝合金箔(总厚度为40μm),Mg AL合金箔层中,Mg的含量为1.8%,Fe含量为1.4%,Si含量0.1%,Sb含量0.02%,退火处理后,铝合金表面的Mg与AL的析出比值为3.5。
把重均分子量为60000、熔点为75℃,酸值为5mg KOH/g的无水马来酸酐改性聚丙烯溶液和环氧树脂溶液以10:1的固体比例形成溶液型混合物均匀地涂布到半成品的Mg AL合金箔面,干燥后形成粘结层7。
将作为热熔接层8的40μm CPP(同实施例1)薄膜表面进行电晕处理,然后将其与粘结层7在100℃温度下热复合后,再在40℃下熟化7天。形成了基材层(25μm)/粘结层(3μm)/铝合金箔层(40μm)/粘结层(3μm)/热熔接层(40μm)的复合成品。
同时,在基材层表面涂上了与实施例1同样量的Slip剂。
实施例8
基材层:
基材层采用厚度为25μm的2段式异步双向拉伸尼龙膜。
铝合金箔层:
采用单层铝合金箔层,厚度为40μm,Mg含量为1%,Fe含量为1.2%,Si含量0.15%,Sb含量0.01%,退火处理后,铝合金表面的Mg与AL的析出比值为2。
采用实施例1中方法制备了基材层(25μm)/粘结层(3μm)/铝合金箔层(40μm)/粘结层(1.5μm)/热熔接层(40μm)的复合成品。同时,也在基材层表面涂上了同样量的Slip剂。
对比例1
基材层:
基材层采用厚度为25μm的2段式异步双向拉伸尼龙膜。
铝合金箔层:
使用的铝合金铝为经过热处理后退火的8021铝箔,铝箔厚度为40μm,Fe含有率为1.4%,Si含量0.1%。
采用实施例1中方法制备了基材层(25μm)/粘结层(3μm)/铝合金箔层(40μm)/粘结层(1.5μm)/热熔接层(40μm)的复合成品。同时,也在基材层表面涂上了同样量的Slip剂。
对比例2
基材层:
基材层采用厚度为25μm的2段式异步双向拉伸聚对苯二甲酸丁二醇酯(PBT)膜。
铝合金箔层:
使用的铝合金铝为经过热处理但未退火处理的3004系铝箔,铝箔厚度为40μm,Mg含有率为1.2%,Fe含有率为0.7%,Mn含量1.2%,Si含量0.3%,铝合金表面的Mg与AL的析出比值为1/5。
采用实施例4中的方法制备出基材层(25μm)/粘结层(3μm)/铝合金箔层(40μm)/粘结层(20μm)/热熔接层(20μm)的复合成品。
同时,在基材层表面涂上了与实施例1同样量的Slip剂。
对比例3
基材层:
基材层采用厚度为25μm的2段式异步双向拉伸聚对苯二甲酸丁二醇酯(PBT)膜。
铝合金箔层:
使用的铝合金铝为经过热处理但未退火处理的5052系铝箔,铝箔厚度为100μm,Mg含有率为2.5%,Fe含有率为0.4%,Cr含有率为0.2%,Si含量0.2%,铝合金表面的Mg与AL的析出比值为11/20。
采用实施例1中方法制备了基材层(25μm)/粘结层(3μm)/铝合金箔层(100μm)/粘结层(1.5μm)/热熔接层(40μm)的复合成品。同时,也在基材层表面涂上了同样量的Slip剂。
关于实施例1-8及对比列1-3的测试结果,如下述表2所示。
表2性能测试表
备注:O表示有电流流动,×表示无电流流动;△表示有Li-AL合金生成,□表示无Li-AL合金生成
由上表可以看出:
由实施例1-8与对比例1对比可以看出,8021系铝箔在耐电解液测试中有电流流动和Li-AL合金生成,发生了腐蚀行为,而实施例1-7均未发生腐蚀行为,表明Mg的存在和析出表面可以提高铝塑复合膜的耐电解液性;
由实施例2、4、5-7与对比例1对比可以看出,8021系铝箔在冲深和拉伸测试中表现没有含有相同Fe含量的实施例2和4中的铝合金箔好,表明提高Sb的含量或降低Si的含量有利于铝合金箔的细晶化,提高铝合金箔的力学性能;
由实施例4与对比例2对比可以看出,较高的Fe和Sb含量,较低的Si含量,降低了其硬度和强度,有利于铝合金箔的细晶化,提高了铝合金箔的伸缩性和成型性。
由实施例1-8与对比例3对比可以看出,5052系铝箔在耐电解液测试中有电流流动和有Li-AL合金生成,表明发生腐蚀行为,故Mg的存在和大比例析出表面可以提高铝塑复合膜的耐电解液性;
由实施例5与对比例3对比可以看出,较低的Fe和Sb含量,较高的Si含量,提高了其硬度和强度,但不利于铝合金箔的细晶化,降低了铝合金箔的伸缩性和成型性。
以上涉及到原料及常规方法皆为公知常识,这里不作详细描述,本领域的技术人员能够理解。
以上所述仅为本发明的一些具体实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。本项发明的技术性范围并不局限于说明书上的内容,必须要根据权利要求范围来确定其技术性范围。
Claims (11)
1.一种电池装置用外包装材料,其特征在于:包括基材层、阻隔层、热熔接层;所述阻隔层是由铝合金箔组成,所述铝合金箔是由单层或多层构成;所述铝合金箔其成分及其质量百分比包括Fe含量在1.2%-2%,Mg含量在1%-2%, Si含量为0.01%-0.2%;所述铝合金箔经退火处理后,析出Mg量与析出AL量的比值在2-4之间。
2.一种电池装置用外包装材料,其特征在于:包括基材层、粘结层、阻隔层、热熔接层;所述粘结层设置在所述基材层和所述阻隔层之间;所述阻隔层是由铝合金箔组成,所述铝合金箔是由单层或多层构成;所述铝合金箔其成分及其质量百分比包括Fe含量在1.2%-2%,Mg含量在1%-2%, Si含量为0.01%-0.2%;所述铝合金箔经退火处理后,析出Mg量与析出AL量的比值在2-4之间。
3.一种电池装置用外包装材料,其特征在于:包括基材层、阻隔层、粘结层、热熔接层;所述粘结层设置在所述阻隔层和所述热熔接层之间;所述阻隔层是由铝合金箔组成,所述铝合金箔是由单层或多层构成;所述铝合金箔其成分及其质量百分比包括Fe含量在1.2%-2%,Mg含量在1%-2%, Si含量为0.01%-0.2%;所述铝合金箔经退火处理后,析出Mg量与析出AL量的比值在2-4之间。
4.一种电池装置用外包装材料,其特征在于:包括基材层、第一粘结层、阻隔层、第二粘结层、热熔接层;所述第一粘结层设置在所述基材层和所述阻隔层之间;所述第二粘结层设置在所述阻隔层和所述热熔接层之间;所述阻隔层是由铝合金箔组成,所述铝合金箔是由单层或多层构成;所述铝合金箔其成分及其质量百分比包括Fe含量在1.2%-2%,Mg含量在1%-2%, Si含量为0.01%-0.2%;所述铝合金箔经退火处理后,析出Mg量与析出AL量的比值在2-4之间。
5.根据权利要求1-4任一权利要求所述的电池装置用外包装材料,其特征在于:所述铝合金箔其成分还包括Sb含量为0.02%-0.06%,Mn含量在0.01%以下,Zn含量在0.03%以下,Cr含量在0.01%以下。
6.根据权利要求1-4任一权利要求所述的电池装置用外包装材料,其特征在于:所述铝合金箔的晶粒直径的平均值为10μm以下。
7.根据权利要求1-4任一权利要求所述的电池装置用外包装材料,其特征在于:所述铝合金箔中占全体90%以上的晶粒尺寸分布在直径0.01~30μm。
8.根据权利要求1-4任一权利要求所述的电池装置用外包装材料,其特征在于:所述铝合金箔的厚度在20-100μm之间。
9.根据权利要求1-4任一权利要求所述的电池装置用外包装材料,其特征在于:至少与热熔接层复合的阻隔层表面经过耐腐蚀处理,耐腐蚀剂成分包括氨基苯酚、聚丙烯酸和改性聚烯烃,处理方式包括硝酸铬盐处理、磷酸铬盐处理和铈处理,耐腐蚀层的厚度在2μm以下。
10.根据权利要求1-4任一权利要求所述的电池装置用外包装材料,其特征在于:所述热熔接层由单层或多层的改性聚丙烯、聚丙烯或聚烯烃组成,厚度在20-120μm。
11.一种电池,其特征在于:使用如权利要求1-10中任一种电池装置用外包装材料。
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CN111653694B (zh) * | 2020-05-21 | 2021-08-06 | 上海恩捷新材料科技有限公司 | 一种电池装置用外包装材料及电池 |
CN113517504B (zh) * | 2020-12-07 | 2022-08-02 | 江西睿捷新材料科技有限公司 | 一种金属复合膜及其电化学装置 |
CN113036271B (zh) * | 2021-02-04 | 2022-06-21 | 厦门大学 | 一种耐电解液、抗剥离铝塑膜及其制备方法和电池 |
CN113059884A (zh) * | 2021-03-17 | 2021-07-02 | 上海恩捷新材料科技有限公司 | 一种电池元件用高成型且耐久性优异的外包装材料及电池 |
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CN114678637B (zh) * | 2022-04-18 | 2023-12-08 | 江苏睿捷新材料科技有限公司 | 一种锂离子电池包装用铝塑复合膜及电池 |
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