CN110828713A - 一种锂电池软包装用高阻隔铝塑膜及制备方法 - Google Patents
一种锂电池软包装用高阻隔铝塑膜及制备方法 Download PDFInfo
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Abstract
本发明涉及锂电池技术领域，公开了一种锂电池软包装用高阻隔铝塑膜及制备方法。包括如下制备过程：（1）将蒸镀基材经过清洗后送入蒸镀铝室，使用电流高频加热，同时从下至上由气流送入石墨烯，石墨烯掺杂的铝蒸气接触蒸镀基材后冷却沉积在基材表面，制得铝/石墨烯共蒸镀层；（2）由外至内依次为PA流延膜外保护层、铝/石墨烯共蒸镀层、CPP流延膜热封层的顺序层叠复合，热定型，制得用于锂电池软包装的高阻隔铝塑膜。本发明制得的铝塑膜的铝箔层的内部针孔数量少、阻隔性好、耐化学性好，得到的锂电池铝塑膜耐穿刺性更好、水气阻隔性更高、密封性好、安全性更强、使用寿命更长。
Description
技术领域
本发明涉及锂电池技术领域，公开了一种锂电池软包装用高阻隔铝塑膜及制备方法。
背景技术
迄今为止，锂电池以高能量密度、优越的高低温环境适应能力被广泛地应用于各类小型数码产品中。其采用的包装从中低端的硬质钢壳、铝壳逐渐更换为软质铝塑膜外包装。铝塑膜作为锂电池的外包装袋具有柔韧性，可以释放锂电池在使用过程中意外释放气体产生的增压，防止电池爆炸。该膜材通常有高水汽阻隔性的铝箔与具有良好耐化学性、热封性和柔韧性的塑料膜复合而成。
目前广泛所使用的铝塑膜分为三层：内层为粘结层，多采用聚乙烯或聚丙烯材料，起封口粘结作用；中间层为铝箔，能够防止电池外部水汽的渗入，同时防止内部电解液的渗出；外层为保护层，有很强的机械性能，防止外力对电池的损伤，起保护电池的作用。
对于锂离子电池来说，铝塑膜主要提供包装和密封两种作用，同时还有具有一定的机械作用。对于铝塑膜的密封性来说，一方面要是隔绝空气中的氧气进入电池内部，另一方面是隔绝电解液透过聚丙烯薄膜层腐蚀铝箔。锂离子电池使用的铝塑包装膜主要由外侧的尼龙层、中间的铝箔层、内侧的PP层以及各层之间的高分子树脂粘结剂组成，其中各层均由单独的工厂分别生产，最后由铝塑膜制造厂家把这几种材料复合在一起，制作成锂离子电池用的铝塑包装膜。
中国发明专利申请号201310104306.7公开了一种新型锂电池用铝塑膜，包括保护层、化学处理层Ⅰ、中间铝箔、化学处理层Ⅱ和热封层，所述的化学处理层Ⅰ和化学处理层Ⅱ是采用铬盐、酸、氟化物的混合溶液对中间铝箔表面进行化学处理，在中间铝箔表面形成的致密金属氧化物膜层，将保护层、经化学处理过的中间铝箔和热封层通过热帖复合机一次成型热帖复合。
中国发明专利申请号201520080428.1公开了一种高密封性的大型锂电池铝塑膜，大型锂电池铝塑膜具有层状结构，由上至下依次包括PET流延膜外保护层、第一粘合层、PA流延膜外保护层、第二粘合层、铝箔层、第三粘合层、镀铝膜、第四粘合层和CPP流延膜热封层，其中镀铝膜包括蒸镀基材层和蒸镀在蒸镀基材层上的镀铝层，所述镀铝层朝向所述铝箔层的一侧。该实用新型通过铝箔层与镀铝膜合用粘合作为阻隔层，其中镀铝膜中的镀铝层不显著提高铝材用量，但与铝箔层合用显著地提高了铝塑膜的阻隔性和包装锂电池后的密封性。
根据上述，现有方案中用于锂电池封装铝塑膜虽然具有较高的耐化学性、隔湿、隔氧、封装粘结力并能防爆，但是其中起阻隔性、防潮性、遮光性的铝箔在厚度较薄特别是如0.2mm以下时多带有不可避免的透光小孔，俗称针孔，针孔的存在严重影响铝箔的阻隔性和耐化学性，进而影响铝塑膜作为锂电池外袋材料的密封性，本发明提出了一种锂电池软包装用高阻隔铝塑膜及制备方法，可有效解决上述技术问题。
发明内容
目前应用较广的用于锂电池包装的铝塑膜中，铝箔存在不可避免的针孔进而严重影响铝箔的阻隔性和耐化学性等缺点。
本发明通过以下技术方案达到上述目的：
一种锂电池软包装用高阻隔铝塑膜的制备方法，制备的具体过程为：
（1）选用PA流延膜作为共蒸镀层的蒸镀基材，经过清洗后送入蒸镀铝室内，然后使用电流高频加热的方法对蒸镀铝室进行加热，使蒸镀铝室充满铝蒸气，同时从下至上由气流送入石墨烯，承镀层的PA流延膜基材紧贴在蒸镀铝室上方的冷却辊上，石墨烯掺杂的铝蒸气接触蒸镀基材后冷却沉积在基材表面，制得铝/石墨烯共蒸镀层；
（2）以由外至内依次为PA流延膜外保护层、铝/石墨烯共蒸镀层、CPP流延膜热封层的顺序层叠复合，热压定型，制得用于锂电池软包装的高阻隔铝塑膜。
以PA流延膜为基材进行蒸镀滤膜，可得到耐折性和韧性优良的铝塑膜，同时可大大减少铝的用量，通过在蒸镀铝箔的过程中掺入石墨烯片，石墨烯是一种二维晶体，具有优异的化学和物理性质，可在铝塑膜层状结构中形成改性高阻隔铝箔层，由于铝箔层中分散有石墨烯片，有效减少了内部的针孔数量，可有效防止锂电池外部的水汽由铝箔的针孔进入，提升铝箔的阻隔性和耐化学性，从而显著提高铝塑膜的阻隔性和包装锂电池后的密封性。作为本发明的优选，步骤（1）所述蒸镀铝室的加热温度为1400~1800℃，所述铝蒸气中石墨烯的掺杂浓度为5~8%。
优选的，步骤（1）所述冷却辊的温度为-80~-5℃。
优选的，所述热压定型采用140-160℃的温度热压定型，在加热和辊间常规压力下CPP流延膜层与铝/石墨烯共蒸镀层粘合粘接。
由上述方法制备得到的一种锂电池软包装用高阻隔铝塑膜，所述高阻隔铝塑膜由外至内依次由PA流延膜外保护层、铝/石墨烯共蒸镀层、CPP流延膜热封层组成。
优选的，所述PA流延膜外保护层的厚度为15~35μm。
优选的，所述铝/石墨烯共蒸镀层的厚度为5~10μm。
优选的，所述CPP流延膜热封层的厚度为20~40μm。
本发明上述方法得到的一种锂电池软包装用高阻隔铝塑膜，其不但具有良好的耐穿刺性，而且阻隔性好，用于锂电池包装时密封性好，安全性高。
本发明提供的一种锂电池软包装用高阻隔铝塑膜及制备方法，选用PA流延膜为共蒸镀层的蒸镀基材，经过清洗后送入蒸镀铝室内，使用电流高频加热的方法将蒸镀铝室温度加热，使蒸镀铝室充满铝蒸气，同时从下至上由气流送入石墨烯，承镀层的PA流延膜基材紧贴在蒸镀铝室上方的冷却辊上，石墨烯掺杂铝蒸气接触蒸镀基材后冷却沉积在其表面；以由外至内依次为PA流延膜外保护层、铝/石墨烯共蒸镀层、CPP流延膜热封层的顺序层叠复合。
本发明提供了一种锂电池软包装用高阻隔铝塑膜及制备方法，与现有技术相比，其突出的特点和优异的效果在于：
1、提出了蒸镀铝箔时掺入石墨烯片制备锂电池软包装用高阻隔铝塑膜的方法。
2、通过在铝塑膜层状结构中形成石墨烯改性高阻隔铝箔层，可有效减少内部的针孔数量，并防止锂电池外部的水汽由铝箔的针孔进入，提升了铝箔的阻隔性和耐化学性，从而显著提高了铝塑膜的阻隔性和包装锂电池后的密封性。
3、本发明制得的锂电池铝塑膜耐穿刺性更好、水气阻隔性更高、安全性更强、使用寿命更，具有良好的应用前景。
具体实施方式
以下通过具体实施方式对本发明作进一步的详细说明，但不应将此理解为本发明的范围仅限于以下的实例。在不脱离本发明上述方法思想的情况下,根据本领域普通技术知识和惯用手段做出的各种替换或变更,均应包含在本发明的范围内。
实施例1
（1）选用PA流延膜作为共蒸镀层的蒸镀基材，经过清洗后送入蒸镀铝室内，然后使用电流高频加热的方法对蒸镀铝室进行加热，使蒸镀铝室充满铝蒸气，同时从下至上由气流送入石墨烯，承镀层的PA流延膜基材紧贴在蒸镀铝室上方的冷却辊上，石墨烯掺杂的铝蒸气接触蒸镀基材后冷却沉积在基材表面，制得铝/石墨烯共蒸镀层；蒸镀铝室的加热温度为1600℃；冷却辊的温度为-40℃；铝蒸气中石墨烯的掺杂浓度为8%；铝蒸气中石墨烯的掺杂浓度为8%；
（2）以由外至内依次设置PA流延膜外保护层、铝/石墨烯共蒸镀层、CPP流延膜热封层的顺序层叠复合，通过辊压在150℃压合，制得用于锂电池软包装的高阻隔铝塑膜。
所述PA流延膜外保护层的厚度为15μm；所述铝/石墨烯共蒸镀层的厚度为8μm；所述CPP流延膜热封层的厚度为30μm。
实施例2
（1）选用PA流延膜作为共蒸镀层的蒸镀基材，经过清洗后送入蒸镀铝室内，然后使用电流高频加热的方法对蒸镀铝室进行加热，使蒸镀铝室充满铝蒸气，同时从下至上由气流送入石墨烯，承镀层的PA流延膜基材紧贴在蒸镀铝室上方的冷却辊上，石墨烯掺杂的铝蒸气接触蒸镀基材后冷却沉积在基材表面，制得铝/石墨烯共蒸镀层；蒸镀铝室的加热温度为1600℃；冷却辊的温度为-40℃；铝蒸气中石墨烯的掺杂浓度为8%；
（2）以由外至内依次设置PA流延膜外保护层、铝/石墨烯共蒸镀层、CPP流延膜热封层的顺序层叠复合，通过辊压在150℃压合，制得用于锂电池软包装的高阻隔铝塑膜。；
所述PA流延膜外保护层的厚度为15μm；所述铝/石墨烯共蒸镀层的厚度为8μm；所述CPP流延膜热封层的厚度为30μm。
实施例3
（1）选用PA流延膜作为共蒸镀层的蒸镀基材，经过清洗后送入蒸镀铝室内，然后使用电流高频加热的方法对蒸镀铝室进行加热，使蒸镀铝室充满铝蒸气，同时从下至上由气流送入石墨烯，承镀层的PA流延膜基材紧贴在蒸镀铝室上方的冷却辊上，石墨烯掺杂的铝蒸气接触蒸镀基材后冷却沉积在基材表面，制得铝/石墨烯共蒸镀层；蒸镀铝室的加热温度为1400℃；冷却辊的温度为-20℃；铝蒸气中石墨烯的掺杂浓度为5%；
（2）以由外至内依次设置PA流延膜外保护层、铝/石墨烯共蒸镀层、CPP流延膜热封层的顺序层叠复合，通过辊压在150℃压合，制得用于锂电池软包装的高阻隔铝塑膜。
所述PA流延膜外保护层的厚度为15μm；所述铝/石墨烯共蒸镀层的厚度为8μm；所述CPP流延膜热封层的厚度为30μm。
实施例4
（1）选用PA流延膜作为共蒸镀层的蒸镀基材，经过清洗后送入蒸镀铝室内，然后使用电流高频加热的方法对蒸镀铝室进行加热，使蒸镀铝室充满铝蒸气，同时从下至上由气流送入石墨烯，承镀层的PA流延膜基材紧贴在蒸镀铝室上方的冷却辊上，石墨烯掺杂的铝蒸气接触蒸镀基材后冷却沉积在基材表面，制得铝/石墨烯共蒸镀层；蒸镀铝室的加热温度为1400℃；冷却辊的温度为-5℃；铝蒸气中石墨烯的掺杂浓度为6%；
（2）以由外至内依次设置PA流延膜外保护层、铝/石墨烯共蒸镀层、CPP流延膜热封层的顺序层叠复合，通过辊压在150℃压合，制得用于锂电池软包装的高阻隔铝塑膜。
所述PA流延膜外保护层的厚度为15μm；所述铝/石墨烯共蒸镀层的厚度为8μm；所述CPP流延膜热封层的厚度为30μm。
对比例1
对比例1没有添加石墨烯片，其余与实施例1一致。制得的铝塑膜，其耐穿刺强度、透湿性及透氧性如表1所示。
上述性能指标的测试方法为：
（1）耐穿刺强度：参照GB/T10004标准执行本发明制得的铝塑膜的耐穿刺强度测试，试验仪器为TSL铝塑膜耐穿刺性测试仪，钢针球形半径为0.5mm、加载速度为50mm/min；
（2）阻隔性：参照GB/T 1037 塑料薄膜片材水蒸气透过性式样方法在35℃，90%RH湿度，使铝塑复合膜形成湿度差，水蒸气透过透湿杯中的试样进入干燥的一侧，通过测定透湿杯重量随时间的变化量，从而求出试样的水蒸气透过率等参数。
表1：
Claims (7)
1.一种锂电池软包装用高阻隔铝塑膜的制备方法，其特征在于，制备的具体过程为：
（1）选用PA流延膜作为共蒸镀层的蒸镀基材，经过清洗后送入蒸镀铝室内，然后使用电流高频加热的方法对蒸镀铝室进行加热，使蒸镀铝室充满铝蒸气，同时从下至上由气流送入石墨烯，承镀层的PA流延膜基材紧贴在蒸镀铝室上方的冷却辊上，石墨烯掺杂的铝蒸气接触蒸镀基材后冷却沉积在基材表面，制得铝/石墨烯共蒸镀层；
（2）以由外至内依次为PA流延膜作保护层、铝/石墨烯共蒸镀层、CPP流延膜热封层的顺序层叠复合，热压定型，制得用于锂电池软包装的高阻隔铝塑膜。
2.根据权利要求1所述一种锂电池软包装用高阻隔铝塑膜的制备方法，其特征在于：步骤（1）所述蒸镀铝室的加热温度为1400~1800℃。
3.根据权利要求1所述一种锂电池软包装用高阻隔铝塑膜的制备方法，其特征在于：步骤（1）所述冷却辊的温度为-80~-5℃。
4.根据权利要求1所述一种锂电池软包装用高阻隔铝塑膜的制备方法，其特征在于：步骤（1）所述铝蒸气中石墨烯的掺杂浓度为5~8wt%。
5.根据权利要求1所述一种锂电池软包装用高阻隔铝塑膜的制备方法，其特征在于：步骤（2）所述热压定型采用140-160℃的温度热压定型。
6.权利要求1~5任一项所述方法制备得到的一种锂电池软包装用高阻隔铝塑膜，其特征在于：所述高阻隔铝塑膜由外至内依次由PA流延膜外保护层、铝/石墨烯共蒸镀层、CPP流延膜热封层组成。
7.根据权利要求6所述一种锂电池软包装用高阻隔铝塑膜，其特征在于：
所述PA流延膜外保护层的厚度为15~35μm；
所述铝/石墨烯共蒸镀层的厚度为5~10μm；
所述CPP流延膜热封层的厚度为20~40μm。
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| CN114228204A (zh) * | 2021-11-01 | 2022-03-25 | 苏州睿锂物联科技有限公司 | 一种锂电池软包装用高阻隔铝塑膜加工装置 |
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| CN114228204A (zh) * | 2021-11-01 | 2022-03-25 | 苏州睿锂物联科技有限公司 | 一种锂电池软包装用高阻隔铝塑膜加工装置 |
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