CN110400892A - 内嵌式加热功能的锂离子电池软包装塑膜及其制备方法 - Google Patents

内嵌式加热功能的锂离子电池软包装塑膜及其制备方法 Download PDF

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CN110400892A
CN110400892A CN201910532464.XA CN201910532464A CN110400892A CN 110400892 A CN110400892 A CN 110400892A CN 201910532464 A CN201910532464 A CN 201910532464A CN 110400892 A CN110400892 A CN 110400892A
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material layer
layer
polymer material
lithium ion
ion battery
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吴战宇
刘国强
姜庆海
施晓渝
毛旭辉
张孝杰
单丹
王大林
成辰
蒋仕平
沙树勇
朱明海
董志成
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Huafu (jiangsu) Lithium Electricity New Technology Co Ltd
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Abstract

本发明公开了内嵌式加热功能的锂离子电池软包装塑膜及其制备方法，该软包装塑膜依次包括外部高分子材料层、加热膜层、金属材料层和内部高分子材料层，加热膜层设置有正极端子和负极端子，正极端子和负极端子从加热膜层垂直穿透外部高分子材料层延伸到其外部表面，并向上鼓起，形成球面体结构。该方法包括对外部高分子材料层和内部高分子材料层的单面及加热膜层双面进行等离子电晕处理；对金属材料层双面进行铬化处理；在外部高分子材料层和内部高分子材料层的处理面、金属材料层单面分别涂覆粘结剂，按上述次顺层叠顺序进行层压复合、干燥。本发明加热功能整合至电池外包装塑膜内部，可对整个电池进行加热。

Description

内嵌式加热功能的锂离子电池软包装塑膜及其制备方法
技术领域
本发明涉及内嵌式加热功能的锂离子电池软包装塑膜及其制备方法，属于化学电源材料技术领域。
背景技术
软包装塑膜是软包聚合物锂离子电池的封装材料，其阻隔能力、耐穿刺能力、电解液稳定性、耐高温性和绝缘性等影响着锂离子电池的使用性能。目前可见的塑膜均不具备加热功能，这使锂离子电池在低温环境下的应用受到了影响。锂离子电池在低温时，特别是在0℃以下时，放电容量会明显降低，且无法充电，如果在0℃以下强行充电，会使锂离子电池内部产生析锂现象，造成锂离子电池寿命终止，严重时会鼓胀、起火甚至发生爆炸。
有人进行了软包装塑膜的研究，例如专利201510407891.7公开了一种高性能锂电池复合包装铝塑膜及制备方法，该铝塑膜具有层状结构，由内到外依次为改性聚丙烯层、第一胶粘剂层、铝箔层、第二胶粘剂层、聚乙烯层、第三胶粘剂层、聚对苯二甲酸聚酯层；专利201810777956.0公开了一种改性尼龙膜、其制备方法及锂离子电池软包装铝塑膜，利用经过纳米纤维素改性的水性聚氨酯溶液对尼龙膜进行改性，一定程度上起到补强增韧的作用，提高尼龙膜的强度和耐酸性能；专利201720634779.1提供了一种软包装锂离子电池用铝塑膜，采用力学性能良好的石墨烯薄膜，提高散热性能，从而提高电池的寿命和安全能够散热。从已经公开的方法可见，目前的软包装塑膜只是针对所用材料的进行改变，并无加热功能，也没有使用内嵌有加热膜的软包装塑膜。无加热功能，使锂离子电池的应用温度受到限制，必须在0℃以上环境下充电；普通锂电池要想在低温环境下使用，则必须进行环境加热以保持0℃以上，或者对单体电芯进行加热（如外覆加热膜等手段），但对单体电池加热往往会造成电芯之间受热不均，无法实现整体温度一致。
也有人进行了锂离子电池加热的研究，例如专利201610472033.5公开了一种锂离子电池模组热平衡管理系统，包括导热结构件、形变导热垫、加热膜、散热片、均衡和温度控制电路板、电池管理系统电路板，加热膜布置于长方体电池模组两个较宽的面中的其中一个面；专利201611071651.5公开了一种带加热模块的锂离子电池模组，它包括锂电池组模块和加热模块，加热模块的电加热布包裹在锂电电芯组的外壁上。从已经公开的方法可见，目前的加热方案主要是针对电池成组后，在电池组的外部包裹加热装置，无法实现对单只电芯的加热，存在加热不均匀，电池组内温度不均匀的弊端。
发明内容
为了解决上述存在的问题，本发明公开了一种内嵌式加热功能的锂离子电池软包装塑膜及其制备方法，微米级电加热膜层内嵌置锂离子电池软包装塑膜内，形成了具有加热功能的锂离子电池软包装塑膜。其具体技术方案如下：
内嵌式加热功能的锂离子电池软包装塑膜，从锂离子电池软包装塑膜外侧到内侧依次包括外部高分子材料层、加热膜层、金属材料层和内部高分子材料层，所述加热膜层设置有正极端子和负极端子，所述正极端子和负极端子从加热膜层垂直穿透外部高分子材料层延伸到其外部表面，并向上鼓起，形成球面体结构。
进一步的，所述外部高分子材料层和加热膜层之间通过第一粘结剂层粘结，加热膜层和金属材料层之间通过第二粘结剂层粘结，金属材料层和内部高分子材料层之间通过第三粘结剂层粘结。
进一步的，所述加热膜层的厚度为2~50μm。
进一步的，所述外部高分子材料层、第一粘结剂层、加热膜层、第二粘结剂层、金属材料层、第三粘结剂层和内部高分子材料层的总厚度为30~200μm。
进一步的，所述金属材料层选用铝箔金属层或者铝合金箔金属层；
所述加热膜层选用微米级碳纤维加热膜或者石墨烯加热膜；
所述外部高分子材料层选用尼龙、聚对苯二甲酸乙二酯、聚萘二甲酸乙二酯中的一种或任意种组合；
所述内部高分子材料层选用聚乙烯及其共聚物、聚丙烯及其共聚物、改性聚乙烯、改性聚丙烯、氯化聚乙烯、氯化聚丙烯的一种或任意种组合；
所述第一粘结剂层、第二粘结剂层和第三粘结剂层分别选用乙烯-醋酸乙烯共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸甲酯共聚物、马来酸酐或丙烯酸改性的聚乙烯及其共聚物、马来酸酐或丙烯酸改性的聚丙烯及其共聚物、马来酸酐或丙烯酸改性的乙烯-醋酸乙烯共聚物、马来酸酐或丙烯酸改性的乙烯-丙烯酸共聚物、马来酸酐或丙烯酸改性的乙烯-丙烯酸甲酯共聚物的一种或任意种组合。
内嵌式加热功能的锂离子电池软包装塑膜的制备方法，包括以下步骤：
步骤一：准备基材：选取外部高分子材料层、加热膜层、金属材料层和内部高分子材料层，将其裁切，各层基材的规格一致；
步骤二：预处理：对外部高分子材料层单面、内部高分子材料层单面及加热膜层双面进行等离子电晕处理，分别形成对应的处理面，
对金属材料层双面进行铬化处理；
步骤三：涂胶：在外部高分子材料层处理面、内部高分子材料层处理面、金属材料层的任一单面分别涂覆或喷涂粘结剂；
步骤四：复合：按内部高分子材料层、金属材料层、加热膜层、外部高分子材料层的层叠顺序进行层压复合；
步骤五：干燥：对步骤四得到的复合材料层进行干燥处理，直到粘结剂中的水分气化完全。
进一步的，所述步骤四中，内部高分子材料层、金属材料层、加热膜层、外部高分子材料层的层叠顺序摆放完毕后，从其一面垂直朝向复合材料层整体施压，压力逐渐增加，直到复合材料层四周挤出均匀连贯的粘结剂，并停留保持压力，直到挤出的粘结剂凝固完全。
进一步的，所述步骤五采用干法干燥。
进一步的，当金属材料层选用铝箔金属层时，金属材料层与内部高分子材料层之间的粘结剂用马来酸酐改性聚丙烯时，步骤四中金属材料层与内部高分子材料层复合前，首先对金属材料层与内部高分子材料层进行缓慢升温加热，温度升至160摄氏度以下，开始对复合叠放的各材料层进行整体升压热压。
进一步的，所述步骤一中，选定对应规格后，在外部高分子材料层的对应位置钻孔，该钻孔的位置为外部高分子材料层与加热膜层边缘对齐时，正极端子和负极端子对应的位置，且正极端子和负极端子能够从对应的钻孔中穿过。
本发明的有益效果是：
本专利将加热功能整合至电池外包装塑膜内部，加热膜可整体覆盖电池，加热时可对整个电池进行加热，电池受热均匀，从而实现加热均匀。
本发明有效解决软包装锂离子电池在低温环境下的易析锂、容量降低、循环寿命短等弊端（原因是低温时（0℃以下），锂离子电池嵌锂脱锂能力变差，低温充电会造成析锂，析锂之后电池内部活性物质结构受到不可逆破坏，从而使电池寿命终止。），有效提升了软包装锂离子电池的低温性能。此外，本发明的软包装塑膜制造工艺便于实施，易于生产加工。
附图说明
图1是本发明的纵向剖面图，
图2是本发明的立体图，
附图标记列表：1—外部高分子材料层，2—第一粘结剂层，3—加热膜层，4—第二粘结剂层，5—金属材料层，6—第三粘结剂层，7—内部高分子材料层，8—正极端子，9—负极端子。
具体实施方式
下面结合附图和具体实施方式，进一步阐明本发明。应理解下述具体实施方式仅用于说明本发明而不用于限制本发明的范围。
图1是本发明的纵向剖面图，图中各层厚度并非实际厚度比例关系，仅为示意其存在位置所用，结合附图可见，本内嵌式加热功能的锂离子电池软包装塑膜，从外侧到内侧依次包括：外部高分子材料层1、第一粘结剂层2、加热膜层3、第二粘结剂层4、金属材料层5、第三粘结剂层6、内部高分子材料层7，其中，加热膜层3连接有穿透过外部高分子材料层1和第一粘结剂层2的正极端子8和负极端子9，正极端子8和负极端子9均延伸到外部高分子材料层1的外侧表面，并形成向上拱起的凸包。本发明实现的效果是，在使用过程中，正极端子8和负极端子9处于通电放热的状态，包裹在电池表面，确保锂离子电池的温度得到有效控制，避免出现低温给锂离子电池带来的损伤。
内嵌式加热功能的锂离子电池软包装塑膜的制备方法，包括以下步骤：
步骤一：准备基材：选取外部高分子材料层1、加热膜层3、金属材料层5和内部高分子材料层7，将其裁切，各层基材的规格一致，在外部高分子材料层1的对应位置钻孔，该钻孔的位置为外部高分子材料层1与加热膜层3边缘对齐时，正极端子和负极端子对应的位置，且正极端子和负极端子能够从对应的钻孔中穿过。
步骤二：预处理：对外部高分子材料层1单面、内部高分子材料层7单面及加热膜层3双面进行等离子电晕处理，分别形成对应的处理面，对金属材料层5双面进行铬化处理。
步骤三：涂胶：在外部高分子材料层1处理面、内部高分子材料层7处理面、金属材料层5的任一单面分别涂覆或喷涂粘结剂。
步骤四：复合：内部高分子材料层7、金属材料层5、加热膜层3、外部高分子材料层1的层叠顺序摆放完毕后，从其一面垂直朝向复合材料层整体施压，压力逐渐增加，直到复合材料层四周挤出均匀连贯的粘结剂，并停留保持压力，直到挤出的粘结剂凝固完全。
步骤五：干燥：对步骤四得到的复合材料层进行干法或热法干燥处理，直到粘结剂中的水分气化完全。
当金属材料层5选用铝箔金属层时，金属材料层5与内部高分子材料层7之间的粘结剂用MPP(马来酸酐改性聚丙烯)时，步骤四中金属材料层5与内部高分子材料层7复合前，首先对金属材料层5与内部高分子材料层7进行缓慢升温加热，温度升至160摄氏度以下，开始对复合叠放的各材料层进行整体升压热压，其他材料时，均采用干法干燥。
本发明方案所公开的技术手段不仅限于上述技术手段所公开的技术手段，还包括由以上技术特征任意组合所组成的技术方案。
以上述依据本发明的理想实施例为启示，通过上述的说明内容，相关工作人员完全可以在不偏离本项发明技术思想的范围内，进行多样的变更以及修改。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 (10)

1.内嵌式加热功能的锂离子电池软包装塑膜，其特征在于，从锂离子电池软包装塑膜外侧到内侧依次包括外部高分子材料层（1）、加热膜层（3）、金属材料层（5）和内部高分子材料层（7），所述加热膜层（3）设置有正极端子（8）和负极端子（9），所述正极端子（8）和负极端子（9）从加热膜层（3）垂直穿透外部高分子材料层（1）延伸到其外部表面，并向上鼓起，形成球面体结构。
2.根据权利要求1所述的内嵌式加热功能的锂离子电池软包装塑膜，其特征在于，所述外部高分子材料层（1）和加热膜层（3）之间通过第一粘结剂层（2）粘结，加热膜层（3）和金属材料层（5）之间通过第二粘结剂层（4）粘结，金属材料层（5）和内部高分子材料层（7）之间通过第三粘结剂层（6）粘结。
3.根据权利要求1所述的内嵌式加热功能的锂离子电池软包装塑膜，其特征在于，所述加热膜层（3）的厚度为2~50μm。
4.根据权利要求1所述的内嵌式加热功能的锂离子电池软包装塑膜，其特征在于，所述外部高分子材料层（1）、第一粘结剂层（2）、加热膜层（3）、第二粘结剂层（4）、金属材料层（5）、第三粘结剂层（6）和内部高分子材料层（7）的总厚度为30~200μm。
5.根据权利要求1所述的内嵌式加热功能的锂离子电池软包装塑膜，其特征在于，所述金属材料层（5）选用铝箔金属层或者铝合金箔金属层；
所述加热膜层（3）选用微米级碳纤维加热膜或者石墨烯加热膜；
所述外部高分子材料层（1）选用尼龙、聚对苯二甲酸乙二酯、聚萘二甲酸乙二酯中的一种或任意种组合；
所述内部高分子材料层（7）选用聚乙烯及其共聚物、聚丙烯及其共聚物、改性聚乙烯、改性聚丙烯、氯化聚乙烯、氯化聚丙烯的一种或任意种组合；
所述第一粘结剂层（2）、第二粘结剂层（4）和第三粘结剂层（6）分别选用乙烯-醋酸乙烯共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸甲酯共聚物、马来酸酐或丙烯酸改性的聚乙烯及其共聚物、马来酸酐或丙烯酸改性的聚丙烯及其共聚物、马来酸酐或丙烯酸改性的乙烯-醋酸乙烯共聚物、马来酸酐或丙烯酸改性的乙烯-丙烯酸共聚物、马来酸酐或丙烯酸改性的乙烯-丙烯酸甲酯共聚物的一种或任意种组合。
6.内嵌式加热功能的锂离子电池软包装塑膜的制备方法，其特征在于，包括以下步骤：
步骤一：准备基材：选取外部高分子材料层（1）、加热膜层（3）、金属材料层（5）和内部高分子材料层（7），将其裁切，各层基材的规格一致；
步骤二：预处理：对外部高分子材料层（1）单面、内部高分子材料层（7）单面及加热膜层（3）双面进行等离子电晕处理，分别形成对应的处理面，
对金属材料层（5）双面进行铬化处理；
步骤三：涂胶：在外部高分子材料层（1）处理面、内部高分子材料层（7）处理面、金属材料层（5）的任一单面分别涂覆或喷涂粘结剂；
步骤四：复合：按内部高分子材料层（7）、金属材料层（5）、加热膜层（3）、外部高分子材料层（1）的层叠顺序进行层压复合；
步骤五：干燥：对步骤四得到的复合材料层进行干燥处理，直到粘结剂中的水分气化完全。
7.根据权利要求6所述的内嵌式加热功能的锂离子电池软包装塑膜的制备方法，其特征在于，所述步骤四中，内部高分子材料层（7）、金属材料层（5）、加热膜层（3）、外部高分子材料层（1）的层叠顺序摆放完毕后，从其一面垂直朝向复合材料层整体施压，压力逐渐增加，直到复合材料层四周挤出均匀连贯的粘结剂，并停留保持压力，直到挤出的粘结剂凝固完全。
8.根据权利要求6所述的内嵌式加热功能的锂离子电池软包装塑膜的制备方法，其特征在于，所述步骤五采用干法干燥。
9.根据权利要求6所述的内嵌式加热功能的锂离子电池软包装塑膜的制备方法，其特征在于，当金属材料层（5）选用铝箔金属层时，金属材料层（5）与内部高分子材料层（7）之间的粘结剂用马来酸酐改性聚丙烯时，步骤四中金属材料层（5）与内部高分子材料层（7）复合前，首先对金属材料层（5）与内部高分子材料层（7）进行缓慢升温加热，温度升至160摄氏度以下，开始对复合叠放的各材料层进行整体升压热压。
10.根据权利要求6所述的内嵌式加热功能的锂离子电池软包装塑膜的制备方法，其特征在于，所述步骤一中，选定对应规格后，在外部高分子材料层（1）的对应位置钻孔，该钻孔的位置为外部高分子材料层（1）与加热膜层（3）边缘对齐时，正极端子和负极端子对应的位置，且正极端子和负极端子能够从对应的钻孔中穿过。
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US11621108B2 (en) 2020-12-28 2023-04-04 Littelfuse, Inc. PPTC tank heater
US11670440B2 (en) 2020-12-28 2023-06-06 Littelfuse, Inc. PPTC actuator heater

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Application publication date: 20191101