CN109263220B - 非极性物理锚固法聚合物软包电池铝塑膜及其制造方法 - Google Patents
非极性物理锚固法聚合物软包电池铝塑膜及其制造方法 Download PDFInfo
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Abstract
本发明涉及一种非极性物理锚固法聚合物软包电池铝塑膜及其制造方法。该铝塑膜从内到外依次包括聚丙烯层、聚丙烯与环烯烃类共聚物改性层、等离子体物理锚固一层、等离子物理锚固二层、铝箔层、等离子体物理锚固三层、等离子体物理锚固四层、聚丙烯与环烯烃类共聚物改性层、改性尼龙层；该铝塑膜具有双向力学性能一致性、较低的界面极性、稳定持续的抗电化学腐蚀和抗极性腐蚀特点，从界面分子结构层面解决了锂电池铝塑膜失效机理问题，同时具有优异的深冲成型性能、热封性能、阻隔性能、延展性、抗腐蚀性及耐穿刺性能，可满足铝塑膜封装锂离子电池，特别是有助于动力锂电池、固态聚合物锂电池大容量、快充放、低衰减、长寿命、高安全的要求。
Description
技术领域
本发明涉及电池软包封装材料领域，特别涉及一种非极性物理锚固法聚合物软包电池铝塑膜。
背景技术
电池所能输出的能量取决于活性物质的比容量和单体电池的电压，金属锂是所有金属中比容量最大的物质，其与碳组成电池对的输出电压可高达3.6V以上，显示其独特的优势，因而锂离子电池呈现快速发展的趋势。
锂离子电池由于其重量轻、容量大、循环寿命长(大于1000次)以及无记忆效应的优势很快在手机、笔记本电脑等电池领域扩展应用。同时，由于金属锂非常活泼，直接用其制成电池安全性很差，因而近几年锂电池已向聚合物锂离子可充电电池方向发展。聚合物锂离子电池内部没有可移动的电解液，电池可以做成极薄的片状和各种形状，甚至单片电池可做到0.6mm厚，因而在对电池轻量化、小量化或对电池形状要求严格的应用领域，聚合物电池都有着更为广泛的应用优势和前景。
聚合物电池最后是通过软包装材料形成电池，软包装材料质量的好坏对电池的各项性能都具有重要影响，若电池中水、氧含量达到一定程度，聚合物锂离子电池容量将变小、电压降增大，充放电和循环寿命均下降严重，最终可导致电池失效，因此软包装材料一般要求具有极好的热封性能、阻隔性能和延展成型性。除此之外，而在聚合物锂电池层压、包装中，内部金属丝有可能穿透包装膜，影响包装膜的阻隔性，从而导致电池阻隔性的下降或失效，因此如何研制高质量且耐穿刺软包装材料对聚合物锂离子电池的稳定运行均十分重要。
发明内容
为解决上述技术问题，本发明提供一种非极性物理锚固法聚合物软包电池铝塑膜，该铝塑膜具有高的耐穿刺性能，同时该铝塑膜具有良好的深冲成型性能、热封性能、阻隔性能和延展性能，用此铝塑膜可做成消费电池及动力电池产品。
本发明的技术方案为：一种非极性物理锚固法聚合物软包电池铝塑膜。该铝塑膜包括聚丙烯层、聚丙烯与环烯烃类共聚物改性层、等离子体物理锚固一层、等离子物理锚固二层、铝箔层、等离子体物理锚固三层、等离子体物理锚固四层、聚丙烯与环烯烃类共聚物改性层、改性尼龙层。
作为本发明的一种优选方案，所述等离子体物理锚固所用的有机无机纳米杂化活性材料的有机活性基团为多个羟基、羰基、硅氧键、硅碳键、氮氧双键、碳碳双键、氮氮三键等含双键或多链或环状的化合物或单体中的一种或多种。
作为本发明的一种优选方案，所述等离子锚固处理的等离子强度为0.1kw～15kw/cm2.s，优选1kw～8kw/cm2.s。
作为本发明的一种优选方案，所述微波固化其特征在于，采用电致或气致贵金属发射微波，所用微波烘箱的微波波长为0.1cm～70cm，优选0.1～10cm。
作为本发明的一种优选方案，所述铝塑膜采用等离子体或微波制造的高能物理能量激发化学官能团充分交联反应，所述交联反应为界面材料之间及界面材料与有机、无机界面之间共同形成立体网状结构。
作为本发明的一种优选方案，所述有机无机纳米杂化活性材料中无机官能团为Si-O、Si-Ti、Co-Si、Ni-Si、Ta-Si、Mo-Si、W-Si、Me-Si、Ti-O、Ti-Cl、Ti-C、Ti-D中的一种或其组合。
作为本发明的一种优选方案，所述微波吸收靶向材料为含双键或环状的极性有机化合物或单体，分子量为10～3000，优选20～100。
一种非极性物理锚固法聚合物软包电池铝塑膜的制备方法，其特征在于，包括以下步骤：
(1)在聚丙烯与环烯烃类共聚物改性层2低温湿法流延或复合到聚丙烯层1表面，经微波预固化，得到表面处理的聚丙烯流延复合物1；
(2)在聚丙烯与环烯烃类共聚物改性层8流延或复合到改性尼龙层9表面，经微波预固化，得到表面处理的尼龙流延复合物9；
(3)在铝箔表面，聚丙烯流延复合物1、尼龙流延复合物9表面分别或同时沉积一层带有微波吸收靶向材料的有机无机纳米杂化活性材料，分别或同时经等离子接枝锚固后，将各层进行复合、层压，形成铝塑膜半成品。
(4)将铝塑膜半成品进行微波辐照交联，并熟化，得到铝塑膜成品。
采用上述技术方案后，本发明的有益效果是：首先，该铝塑膜通过等离子锚固技术和微波接枝技术可有效提高该铝箔的耐腐蚀性能；其次，该铝塑膜通过烯烃合金一体化技术可有效提高铝塑膜的粘结能力，产品综合性能优良，适合电池、电容产品封装中应用。
附图说明
图1为本发明的结构示意图。
其中，1为聚丙烯层；2为聚丙烯与环烯烃类共聚物改性层；3为等离子体物理锚固一层；4为等离子物理锚固二层；5为铝箔层；6为等离子体物理锚固三层；7为等离子体物理锚固四层；8为聚丙烯与环烯烃类共聚物改性层；9为改性尼龙层。
具体实施方式
下面结合具体实施方式，进一步阐明本发明。
实施例
如图1所示，本发明提供了一种非极性物理锚固法聚合物软包电池铝塑膜，包括1为聚丙烯层；2为聚丙烯与环烯烃类共聚物改性层；3为等离子体物理锚固一层；4为等离子物理锚固二层；5为铝箔层；6为等离子体物理锚固三层；7为等离子体物理锚固四层；8为聚丙烯与环烯烃类共聚物改性层；9为改性尼龙层。
所述铝塑膜由内到外依次为1为聚丙烯层；2为聚丙烯与环烯烃类共聚物改性层；3为等离子体物理锚固一层；4为等离子物理锚固二层；5为铝箔层；6为等离子体物理锚固三层；7为等离子体物理锚固四层；8为聚丙烯与环烯烃类共聚物改性层；9为改性尼龙层。
所述等离子体物理锚固所用的有机无机纳米杂化活性材料的有机活性基团为多个羟基、羰基、硅氧键、硅碳键、氮氧双键、碳碳双键、氮氮三键等含双键或多链或环状的化合物或单体中的一种或多种。
所述等离子锚固处理的等离子强度为0.1kw～15kw/cm2.s，优选1kw～8kw/cm2.s。
所述微波固化其特征在于，采用电致或气致贵金属发射微波，所用微波烘箱的微波波长为0.1cm～70cm，优选0.1～10cm。
所述铝塑膜采用等离子体或微波制造的高能物理能量激发化学官能团充分交联反应，所述交联反应为界面材料之间及界面材料与有机、无机界面之间共同形成立体网状结构。
所述有机无机纳米杂化活性材料中无机官能团为Si-O、Si-Ti、Co-Si、Ni-Si、Ta-Si、Mo-Si、W-Si、Me-Si、Ti-O、Ti-Cl、Ti-C、Ti-D中的一种或其组合。
所述微波吸收靶向材料为含双键或环状的极性有机化合物或单体，分子量为10～3000，优选20～100。
一种非极性物理锚固法聚合物软包电池铝塑膜的制备方法，其特征在于，包括以下步骤：
1)在聚丙烯与环烯烃类共聚物改性层2低温湿法流延或复合到聚丙烯层1表面，经微波预固化，得到表面处理的聚丙烯流延复合物1；
2)在聚丙烯与环烯烃类共聚物改性层8流延或复合到改性尼龙层9表面，经微波预固化，得到表面处理的尼龙流延复合物9；
3)在铝箔表面，聚丙烯流延复合物1、尼龙流延复合物9表面分别或同时沉积一层带有微波吸收靶向材料的有机无机纳米杂化活性材料，分别或同时经等离子接枝锚固后，将各层进行复合、层压，形成铝塑膜半成品。
4)将铝塑膜半成品进行微波辐照交联，并熟化，得到铝塑膜成品。本发明的产品经过测定达到以下指标：
1.层间剥离强度及耐腐蚀性测定：根据《GB/T 8808-1988软质复合塑料材料剥离试验方法》测定标准，层间剥离强大于22N/15mm；铝塑膜在85℃电解液浸泡4～1000小时后，层间剥离强度大于10N/15mm；铝塑膜深冲成型做成电芯，注入电解液后密封，在85℃，90％RH的下存放14～82天，层间剥离强度大于10N/15mm；
2.材料深冲性能测定：根据《Q/320507LD001-2016锂电池封装铝塑膜》测定标准，单坑极限深冲深度达到10mm以上，双坑极限深冲深度达到19mm以上；
3.热封性能测定：根据《QB/T 2358-1998塑料薄膜包装袋热封强度试验方法》测定标准，在热封温度180℃-200℃的条件，热封强度达80N/15mm以上。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以作出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (2)
1.一种非极性物理锚固法聚合物软包电池铝塑膜，其特征在于，从内到外依次包括聚丙烯层1、聚丙烯与环烯烃类共聚物改性层2、等离子体物理锚固一层3、等离子体物理锚固二层4、铝箔层5、等离子体物理锚固三层6、等离子体接枝锚固四层7、聚丙烯与环烯烃类共聚物改性层8、改性尼龙层9，其制造方法为：
(1)在聚丙烯与环烯烃类共聚物改性层2低温湿法流延或复合到聚丙烯层1表面，经微波预固化，得到表面处理的聚丙烯流延复合物1；
(2)在聚丙烯与环烯烃类共聚物改性层8流延或复合到改性尼龙层9表面，经微波预固化，得到表面处理的尼龙流延复合物9；
(3)在铝箔表面、聚丙烯流延复合物1、尼龙流延复合物9表面分别或同时沉积一层带有微波吸收靶向材料的有机无机纳米杂化多爪活性材料，分别或同时经等离子接枝锚固后，将各层进行复合、层压，形成铝塑膜半成品；
(4)将铝塑膜半成品进行微波辐照交联，并熟化，得到铝塑膜成品；
等离子体物理锚固采用有机无机纳米杂化活性材料且有机无机纳米杂化活性材料至少为3个活性多爪结构，多爪结构的有机活性基团为多个羟基、羰基、硅氧键、硅碳键、氮氧双键、碳碳双键、氮氮三键中的一种或多种；
等离子体物理锚固一层、等离子体物理锚固二层、等离子体物理锚固三层、等离子体物理锚固四层的等离子锚固处理的等离子强度为0.1kw～15kw/cm2.s；有机无机纳米杂化活性材料中无机官能团为Si-O、Si-Ti、Co-Si、Ni-Si、Ta-Si、Mo-Si、W-Si、Me-Si、Ti-O、Ti-Cl、Ti-C、Ti-D中的一种或其组合；
铝塑膜内层聚丙烯层1至铝箔层5之间形成的是非极性界面层；
铝塑膜外层改性尼龙层9至铝箔层5之间形成的是非极性界面层；
微波固化采用电致或气致贵金属发射微波，所用微波烘箱的微波波长为0.1cm～70cm；
所述铝塑膜采用等离子体或微波制造的高能物理能量激发化学官能团充分交联反应，所述交联反应为界面材料之间及界面材料与有机、无机界面之间共同形成立体网状结构；
所述微波吸收靶向材料为含双键或环状的有机化合物或单体，分子量为10～3000。
2.根据权利要求1中所述的一种非极性物理锚固法聚合物软包电池铝塑膜，以及用此铝塑膜封装的电池、电容及应用此电池、电容的产品。
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