CN110299478B - 一种柔性电池封装材料的制备方法 - Google Patents
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Abstract
本发明涉及柔性电池技术领域，尤其是一种柔性电池封装材料的制备方法；所述制备方法包括以下步骤：将柔性外层薄膜置于真空室内，并将其输送至金属靶材区，采用金属靶材进行磁控溅射加工的方式制成纳米金属层；在纳米金属层上涂布致密膜生成处理剂，放到淋复设备的放卷机构Ⅰ上，放卷输送至淋复机构；将柔性内层原料薄膜放到淋复设备的放卷机构Ⅱ上，并输送到淋复机构；将极性粘合层原料挤出到自修复膜层表面和柔性内层薄膜上；输送到拉伸机构进行结晶取向控制，然后进行收卷；熟化处理；本发明中提出一种新的柔性电池封装材料的制造方法，制造的封装材料，具有良好回弹性、且在制成电池后，能在完全半径为15mm的测试条件下弯曲次数能够达到20000次以上，同时，该封装材料还具有良好的密封隔绝性以及耐电解质腐蚀性能。
Description
技术领域
本发明涉及柔性电池技术领域，尤其是一种柔性电池封装材料的制备方法。
背景技术
智能设备的发展到现在，柔性屏幕已经开始商用，智能设备的柔性化发展也是市场的趋势所在，而市场对于柔性电池的需求会越来越强烈。特别是可穿戴设备的发展，对柔性电池的需求变得急切。。
尽管市场的需求在增加，但可多次弯曲折叠的柔性电池的发展并没有进一步的起色，原因在于现有的电池都是硬块的，不可弯曲的，而从硬到柔，现有的电池从材料到工艺都无法满足。首先柔性电池折叠弯曲的应用要求，使得电芯内部的结构设计和材料选择都需要全新的研发，其次就是封装材料并不能满足其使用要求。
现阶段使用传统的电池封装材料制成电池后，会出现弯折次数不足，数次反复弯曲后出现塑性形变导致折皱的产生，进而挤压甚至刺破电芯，造成严重的安全隐患。因此，在柔性电池研发和推广的技术发展路线上，必须有一款适用于其封装使用，可以达到20000次反复弯曲而不会出现塑性形变，且能够满足电池的基本使用要求的柔性封装材料。
发明内容
本发明的目的是：填补柔性电池的技术空白，提出一种新的柔性材料的制造方法，制造出一种应用于柔性电池的外壳封装，能够达到在15mm弯曲半径的测试条件下反复弯曲20000次以上，并能满足电池封装使用的其他要求的材料。
为解决上述技术问题，本发明采用的技术方案如下：
一种柔性电池封装材料的制备方法，所述制备方法包括以下步骤：
（1）将柔性外层薄膜置于真空室内，并在真空室中放卷通过金属靶材区，将金属加热至蒸发，并将其输送至金属靶材区内，在柔性外层薄膜上利用磁控溅射加工的加工方式沉积一层纳米金属层，得到半成品Ⅰ；
（2）在步骤（1）中的半成品的纳米金属层上涂布致密膜生成处理剂烘干，得到半成品Ⅱ；
（3）将步骤（2）中的半成品Ⅱ处理好的半成品放到淋复设备的放卷机构Ⅰ上，放卷输送至淋复机构；
将柔性内层原料薄膜放到淋复设备的放卷机构Ⅱ上，并输送到淋复机构；将极性粘合层原料挤出到半成品Ⅱ的自修复膜层表面和柔性内层薄膜上，形成自修复膜层-极性粘合层-柔性内层的结构；
在淋膜还没有完全冷却时，温度在120℃以上，输送到拉伸机构进行结晶取向控制，然后输送至收卷机构进行收卷；
（4）步骤（3）中收卷后的材料进行熟化处理。
进一步的，所述步骤（1）中柔性外层薄膜的材料为聚对苯二甲酸乙二醇酯或聚对苯二甲酸丁二醇酯，厚度为10μm~50μm。
进一步的，所述步骤（1）中的金属选用铝、铜、铁、镍其中一种，所述金属丝的纯度为99%，纳米金属层的厚度为100nm~1μm。
进一步的，所述步骤（2）中烘干处理的生产速度控制为10m/min~80m/min，烘干温度控制为50℃~180℃。
进一步的，所述致密膜生成处理剂的质量份组成如下：硫酸锆1-3份、氟化物1-3份、明矾5-9份、有机亚膦酸酯2-3份、去离子水82-91份的混合物。
进一步的，所述步骤（3）中的柔性内层原料使用5μm~50μm的电晕处理后的改性聚丙烯薄膜或聚丙烯薄膜。
进一步的，使用螺杆挤出机挤压并从螺杆挤出机的模头中流延挤出流延至半成品的的电晕处理面上，流延厚度控制为5μm~50μm，极性粘合层原料使用改性聚丙烯。
进一步的，所述步骤（3）中拉伸机构的工作温度为38℃~70℃，拉伸张力控制为100N~4000N；淋复机械的产线速度控制在6m/min~50m/min。
进一步的，所述步骤（4）中熟化处理的熟化时间为6h~96h，熟化温度为40℃~70℃。
采用本发明的技术方案的有益效果是：
本发明中提出一种新的柔性电池封装材料的制造方法，制造的封装材料应用于柔性电池的外壳封装，具有良好回弹性、且在制成电池后弯曲次数能够达到20000次以上，同时，该封装材料还具有良好的密封隔绝性以及耐电解质腐蚀性能。
附图说明
图1为本发明的结构示意图。
图2为现有封装材料的折皱。
图3为实施例3 中的封装材料弯曲试验后的样品。
图中：1放卷机构Ⅰ，2放卷机构Ⅱ，3淋复机构，4拉伸机构，5收卷机构。
具体实施方式
现在结合附图对本发明作进一步详细的说明。这些附图均为简化的示意图，仅以示意方式说明本发明的基本结构，因此其仅显示与本发明有关的构成。
图1为本发明的结构示意图。
图2为现有封装材料的折皱。
图3为实施例3 中的封装材料弯曲试验后的样品。
实施例1
请参阅图1，将柔性外层薄膜置放于真空室内，关闭真空室抽真空，柔性外层原料使用10μm厚度的聚对苯二甲酸乙二醇酯（PET），并在真空室中放卷通过金属靶材区，本实施例中的金属选用镍丝，将99%纯度的镍丝加热至蒸发，并将其输送到金属靶材区内，在柔性外层原料上利用磁控溅射加工的加工方式沉积成一层500nm厚的纳米金属层。
将制好的半成品涂布特殊的致密膜生成处理剂，涂布面为纳米金属层面，并通过加热反应烘干。处理产线的生产速度控制为30m/min，加热反应烘干温度控制为120℃。其中，致密膜生成处理剂的质量份组成如下：硫酸锆1份、氟化物1份、明矾5份、有机亚膦酸酯2份、去离子水91份的混合物。
将处理好的半成品放到淋复设备的放卷机构1上，开始放卷输送至淋复机构3。
将柔性内层原料薄膜放到淋复设备的放卷机构2上，并输送到淋复机构3。柔性内层原料使用40μm的电晕处理后的改性聚丙烯（PP）薄膜。
将极性粘合层原料使用螺杆挤出机挤压并从螺杆挤出机的模头中流延挤出流延至半成品的自修复膜层表面和柔性内层薄膜的电晕处理面上，形成自修复膜层-极性粘合层-柔性内层的结构，流延厚度控制为20μm，极性粘合层原料使用改性聚丙烯（MPP）。
在淋膜还没有完全冷却时，即温度在120℃以上，输送到拉伸机构4进行结晶取向控制。拉伸机构4的工作温度为50℃，拉伸张力控制为2000N。淋复机械的产线速度控制在10m/min。然后输送至收卷机构5进行收卷。
将上述步骤制好的材料放置到烘房中进行熟化处理，熟化时间为48h，熟化温度为60℃。
实施例2
请参阅图1，将柔性外层薄膜置放于真空室内，关闭真空室抽真空，柔性外层原料使用12μm厚度的聚对苯二甲酸丁二醇酯（PBT），并在真空室中放卷通过金属靶材区，本实施例中的金属选用铝丝，将99%纯度的铝丝加热至蒸发，并将其输送到金属靶材区内，在柔性外层原料上利用磁控溅射加工的加工方式沉积成一层150nm厚的纳米金属层。
将制好的半成品涂布特殊的致密膜生成处理剂，涂布面为纳米金属层面，并通过加热反应烘干。处理产线的生产速度控制为40m/min，加热反应烘干温度控制为180℃。其中，致密膜生成处理剂的质量份组成如下：硫酸锆2份、氟化物2份、明矾7份、有机亚膦酸酯2份、去离子水87份的混合物。
将处理 好的半成品放到淋复设备的放卷机构1上，开始放卷输送至淋复机构3。
将柔性内层原料薄膜放到淋复设备的放卷机构2上，并输送到淋复机构3。柔性内层原料使用50μm的电晕处理后的改性聚丙烯薄膜（PE）。
将极性粘合层原料使用螺杆挤出机挤压并从螺杆挤出机的模头中流延挤出流延至半成品的自修复膜层表面和柔性内层薄膜的电晕处理面上，形成自修复膜层-极性粘合层-柔性内层的结构，流延厚度控制为30μm，极性粘合层原料使用改性聚丙烯（MPP）。
在淋膜还没有完全冷却时，即温度在120℃以上，输送到拉伸机构4进行结晶取向控制。拉伸机构4的工作温度为50℃，拉伸张力控制为1000N。淋复机械的产线速度控制在20m/min。然后输送至收卷机构5进行收卷。
将上述步骤制好的材料放置到烘房中进行熟化处理，熟化时间为96h，熟化温度为65℃。
实施例3
请参阅图1，将柔性外层薄膜置放于真空室内，关闭真空室抽真空，柔性外层原料使用50μm厚度的聚对苯二甲酸乙二醇酯（PET），并在真空室中放卷通过金属靶材区，本实施例中的金属选用铜丝，将99%纯度的铜丝加热至蒸发，并将其输送到金属靶材区内，在柔性外层原料上利用磁控溅射加工的加工方式沉积成一层1μm厚的纳米金属层。
将制好的半成品涂布特殊的致密膜生成处理剂，涂布面为纳米金属层面，并通过加热反应烘干。处理产线的生产速度控制为20m/min，加热反应烘干温度控制为100℃。其中，致密膜生成处理剂的质量份组成如下：硫酸锆3份、氟化物3份、明矾9份、有机亚膦酸酯3份、去离子水82份的混合物。
将处理 好的半成品放到淋复设备的放卷机构1上，开始放卷输送至淋复机构3。
将柔性内层原料薄膜放到淋复设备的放卷机构2上，并输送到淋复机构3。柔性内层原料使用30μm的电晕处理后的改性聚丙烯（PP）薄膜。
将极性粘合层原料使用螺杆挤出机挤压并从螺杆挤出机的模头中流延挤出流延至半成品的自修复膜层表面和柔性内层薄膜的电晕处理面上，形成自修复膜层-极性粘合层-柔性内层的结构，流延厚度控制为10μm，极性粘合层原料使用改性聚丙烯（MPP）。
在淋膜还没有完全冷却时，即温度在120℃以上，输送到拉伸机构4进行结晶取向控制。拉伸机构4的工作温度为50℃，拉伸张力控制为4000N。淋复机械的产线速度控制在40m/min。然后输送至收卷机构5进行收卷。
将上述步骤制好的材料放置到烘房中进行熟化处理，熟化时间为96h，熟化温度为55℃。
实施例1-3中制备的电池封装材料与现有软包封装材料的性能测试对比见表1。
表1
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。凡在本发明的精神和原则之内，所做的任何修改、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 (7)
1.一种柔性电池封装材料的制备方法，其特征在于：所述制备方法包括以下步骤：
（1）将柔性外层薄膜置于真空室内，并在真空室中放卷通过金属靶材区，将金属加热至蒸发，并将其输送至金属靶材区内，在柔性外层薄膜上溅射一层致密的纳米金属层，得到半成品Ⅰ；
（2）在步骤（1）中的半成品的纳米金属层上涂布致密膜生成处理剂烘干，得到半成品Ⅱ；
（3）将步骤（2）中的半成品Ⅱ处理好的半成品放到淋复设备的放卷机构Ⅰ上，放卷输送至淋复机构；将柔性内层原料薄膜放到淋复设备的放卷机构Ⅱ上，并输送到淋复机构；将极性粘合层原料挤出到半成品Ⅱ的自修复膜层表面和柔性内层薄膜上，形成自修复膜层-极性粘合层-柔性内层的结构；在淋膜还没有完全冷却时，温度在120℃以上，输送到拉伸机构进行结晶取向控制，然后输送至收卷机构进行收卷；
（4）步骤（3）中收卷后的材料进行熟化处理；
所述步骤（1）中柔性外层薄膜的材料为聚对苯二甲酸乙二醇酯或聚对苯二甲酸丁二醇酯，厚度为10μm~50μm；
所述步骤（2）中烘干处理的生产速度控制为10m/min~80m/min，烘干温度控制为50℃~180℃。
2.根据权利要求1所述的一种柔性电池封装材料的制备方法，其特征在于：所述步骤（1）中的金属选用铝、铜、铁、镍，所述金属纯度为99%，纳米金属层的厚度为100nm~1μm。
3.根据权利要求1所述的一种柔性电池封装材料的制备方法，其特征在于：所述致密膜生成处理剂的质量份组成如下：硫酸锆1-3份、氟化物1-3份、明矾5-9份、有机亚膦酸酯2-3份、去离子水82-91份的混合物。
4.根据权利要求1所述的一种柔性电池封装材料的制备方法，其特征在于：所述步骤（3）中的柔性内层原料使用5μm~50μm的电晕处理后的改性聚丙烯薄膜或聚丙烯薄膜。
5.根据权利要求1所述的一种柔性电池封装材料的制备方法，其特征在于：使用螺杆挤出机挤压并从螺杆挤出机的模头中流延挤出流延至半成品的电晕处理面上，流延厚度控制为5μm~50μm，极性粘合层原料使用改性聚丙烯。
6.根据权利要求1所述的一种柔性电池封装材料的制备方法，其特征在于：所述步骤（3）中拉伸机构的工作温度为38℃~70℃，拉伸张力控制为100N~4000N；淋复机械的产线速度控制在6m/min~50m/min。
7.根据权利要求1所述的一种柔性电池封装材料的制备方法，其特征在于：所述步骤（4）中熟化处理的熟化时间为6h~96h，熟化温度为40℃~70℃。
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