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CN102501419B - 一种聚烯烃多层微多孔膜及其制备方法 - Google Patents

一种聚烯烃多层微多孔膜及其制备方法 Download PDF

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CN102501419B
CN102501419B CN201110382479.6A CN201110382479A CN102501419B CN 102501419 B CN102501419 B CN 102501419B CN 201110382479 A CN201110382479 A CN 201110382479A CN 102501419 B CN102501419 B CN 102501419B
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polyethylene
molecular weight
screw extruder
double screw
layers
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CN102501419A (zh
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王松钊
王辉
蔡朝辉
吴耀根
廖凯明
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Henan Huiqiang New Energy Material Technology Co ltd
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Foshan Jinhui Hi-Tech Photoelectric Material Co Ltd
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Abstract

本发明公开了一种聚烯烃多层微多孔膜及其制备方法，该聚烯烃多层微多孔膜中间层为聚乙烯微多孔膜，两层表面层均是由聚丙烯与具有超高分子量的聚乙烯组成的微多孔膜，中间层的聚乙烯具有1×105至6×105的分子量；表面层的聚丙烯具有1×105至1×106分子量，表面层的聚乙烯具有5×105至5×106分子量；制备方法中，先分别熔融混合中间层的原辅料、表面层的原辅料，将中间层和表面层的原辅料投入双螺杆挤出机中，经过多层共挤模头挤出、冷却，然后拉伸制膜、萃取、定型，制得产品。

Description

一种聚烯烃多层微多孔膜及其制备方法
技术领域
本发明涉及一种由聚乙烯和聚丙烯组成的聚烯烃多层微多孔复合膜及其制备方法。
背景技术
近年来，石油能源资源短缺、国际石油价格飙升以及使用石化能源其造成的环境问题日益严峻，这引起全世界对新的环保能源的重视，为新能源动力电池行业的发展提供了前所未有的机遇。锂离子二次电池由于具有能量密度高、无记忆效应、使用寿命长、循环充放电效率高、对环境污染小等优点，成为广泛应用的新一代电池。综合目前电池的技术发展情况，锂离子二次电池由于其优异的性能，成为新能源动力电池的最佳选择。
锂离子电池隔膜是锂离子电池的重要组成部分，起着隔离电池正负极和允许充放电时锂离子电流通过的重要作用。并且，在锂离子电池由于内部或外部短路造成电池内部电流过大，温度剧升达到一定温度时，隔膜微孔关闭从而切断电池内部电路，保障电池的安全使用。虽然目前锂离子电池隔膜的产品质量较过去已经有了明显的提高，但汽车用锂离子电池对隔膜提出了更高的要求：更好的耐热性，优秀的力学性能等。这些问题关系着隔膜的品质高低，直接影响着电池的容量、寿命和安全性。锂离子电池隔膜的性能的提升是锂离子电池的升级换代的关键，也是新能源动力电池广泛应用的技术关键。
聚烯烃多微孔隔膜由于具有良好的绝缘性能、优良的力学机械性能、较低的闭孔温度和较宽的使用温度等优点，被广泛用作锂离子二次电池隔膜。目前市场上的电池隔膜主要是由聚乙烯和聚丙烯制备的隔膜。单纯的聚乙烯锂电池隔膜虽然具有较低的关闭温度，但其破膜温度也较低，如果电池内部温度超过闭孔温度后继续升高到一定的温度范围，聚乙烯薄膜熔融破裂，电池正负极直接连通，极易引发电池爆炸，电池的安全性不能得到很好的保障；另一方面，单纯的聚丙烯隔膜具有较高的破膜温度，但其关闭温度也相对较高，不利于电路的保护。现有的电池隔膜难以同时兼顾闭孔温度与破膜温度，而且，其透气性、关闭性能和穿刺强度各项性能差，膜的质量难以保证。
包含聚丙烯微多孔层与聚乙烯微多孔层的多层复合隔膜可以有效解决电池隔膜关闭温度与破膜温度难以同时兼顾的难题。美国的Celgard公司使用干法技术生产了膜层结构为PP/PE/PP的三层复合隔膜，克服了以上的技术难点，但干法制备的隔膜孔径大小不均匀，孔隙狭长，制备的隔膜偏厚，膜厚度小于20μm时质量得不到保障，这限制了其在新能源动力电池的进一步应用。公开号为CN1897329A中国专利文献介绍了一种由聚丙烯和聚乙烯构成的多层多孔薄膜，这种薄膜由湿法生产工艺制备，即具有了聚乙烯较低的闭孔温度，又兼具了聚丙烯较高的破膜温度。但是，我们通过深入的研究发现湿法技术制备的聚丙烯层拉伸效果很差，这也是湿法聚丙烯隔膜无法产业化的主要原因。
发明内容
本发明的目的在于克服现有的技术难题，对隔膜的材料结构进行创新设计，实现湿法多层隔膜的产业化，提供一种适合于动力锂离子电池使用的高品质锂离子电池隔膜，具有低闭孔温度、高破膜温度、低的热收缩、高的耐穿刺性能。
一种聚烯烃多层微多孔膜，其包括三层以上的聚烯烃微多孔膜，中间层为聚乙烯微多孔膜，两层表面层均是由聚丙烯与具有超高分子量的聚乙烯组成的微多孔膜；中间层的聚乙烯具有1×105至6×105的分子量；表面层的聚丙烯具有1×105至1×106的分子量，表面层的聚乙烯具有1×106至5×106的分子量。表面层所采用的聚乙烯分子量越高，膜的抗穿刺性能越好。
优选的，中间层的聚乙烯熔点低于135℃，选自高密度聚乙烯、线性低密度聚乙烯、茂金属聚乙烯中的一种或几种混合。高密度聚乙烯是一种结晶度高、非极性的热塑性树指，具有好的化学稳定性以及很好的电性能，特别是绝缘介电强度高，选用其来制备中间微多孔膜层，有助于降低该聚烯烃多层微多孔膜的关闭温度。线性低密度聚乙烯具有较低的软化温度和熔融温度，有强度大、韧性好、刚性大、耐热、耐寒性好等优点，选用其来制备中间微多孔膜层，能提高该聚烯烃多层微多孔膜的电流关闭速度。而选用茂金属聚乙烯作为中间微多孔膜层，还能够强化薄膜的挤出加工性能，使产品质量稳定。
优选的，表面层的聚丙烯熔点大于165℃，其重量占表面层重量的60％-95％；表面层的聚乙烯熔点大于136℃，其重量占表面层重量的5％-40％的重量。
优选的，该聚烯烃多层微多孔膜由三层聚烯烃微多孔膜构成，即其三层结构为(聚丙烯+超高分子量聚乙烯)/聚乙烯/(聚丙烯+超高分子量聚乙烯)。
本发明的另一目的是提供一种聚烯烃多层微多孔膜的制备方法，该方法包括以下步骤：
A、制备表面层材料：将聚丙烯和具有高分子量的聚乙烯与高沸点低分子量的增塑剂在双螺杆挤出机中熔融混合、制成聚合物溶液A；
B、制备中间层材料：将聚乙烯与高沸点低分子量增塑剂在双螺杆挤出机中熔融混合、制成聚合物溶液B；
C、共挤：将聚合物溶液A和聚合物溶液B通过三层ABA型模头汇合在一起从同一模口挤出，并在铸片辊上冷却至室温制成多层凝胶厚片；
D、制膜：将多层凝胶厚片经预热后进行双向拉伸，制成薄膜；
E、萃取、定型：双向拉伸后的薄膜经盛有抽提剂的洗涤槽萃取除去膜内的高沸点低分子量的增塑剂，经干燥、热定型后制得产品。
优选的，步骤A和B所采用的高沸点低分子量的增塑剂选自壬烷、癸烷、煤油、固体石蜡、液体石蜡、大豆油、蓖麻油、二苯醚中的一种或几种混合。
优选的，步骤A的挤出加工温度为180-260℃，步骤B的挤出加工温度为160-240℃，步骤C的冷却速度为40℃/min。
优选的，步骤D的拉伸温度为90-150℃，宽度拉伸4-12倍，长度拉伸3-10倍。
优选的，步骤E所采用的提取剂为烷烃或卤代烃或醚类有机挥发溶剂，增塑剂与抽提剂的重量比为1∶10～100之间，热定型的处理时间为10-120S，温度为90-140℃。
本发明所制得的聚烯烃多层微多孔膜的性质测试方法包括以下：
(1)平均厚度(μm)
通过接触测厚计在30cm的宽度范围内以5mm纵向间隔测量各个多层微孔膜的厚度，并取其平均值。
(2)孔隙率(％)
通过真密度测试仪测量出微多孔膜的真实密度ρ1，通过测量微多孔膜的面积、厚度、重量，从而算出多孔膜的表观密度ρ2，孔隙率P％＝(ρ1-ρ2)/ρ1，从而测算出多层材料的孔隙率。
(3)针刺穿强度(mN/20μm)
当使用带有球形端面(曲率半径R：0.5mm)的直径为1mm的针，以2mm/秒的速率刺各个厚度为T1的多层微孔膜时，测量最大负荷。通过等式L2＝(L1×20)/T1，将所测量出的最大负荷L1转算成在20μm的厚度的最大负荷L2，并且用作针刺穿强度。
(4)透气性
通过透气性测试器对厚度为T1的多层微孔聚烯烃膜测量透气性P1，通过等式P2＝(P1×20)/T1，将根据JIS P8117对厚度为T1的各个多层微孔膜测量出的透气性P1转化成在20μm厚度的透气性P2。
(5)拉伸强度和拉伸伸长率
根据ASTM D882对宽度为10mm的矩形试样测量。
(6)热收缩率(％)
各个多层微孔聚烯烃膜的收缩率为，测量保持聚烯烃膜在105℃温度下达8小时之后在长度方法和宽度方向的收缩率，每个方向均测量5次，并且将测量出的收缩率取平均值。
(7)关闭温度(℃)
通过热机械分析仪(TMA)按如下测量微孔膜的关闭温度：从微孔膜切下5mm×10mm的矩形样品加载到TMA的样品台上，在拉伸模式下将19.6mN的载荷施加到样品上，以5℃/分钟的加热速率对放置样品的区域进行升温，以0.5秒的间隔测量样品的长度变化情况。关闭温度定义为在聚合物熔点附近出现的聚合物型变量拐点处温度。
(8)破膜温度(℃)
通过热机械分析仪(TMA)按如下测量微孔膜的破膜温度：从微孔膜切下5mm×10mm的矩形样品加载到TMA的样品台上，在拉伸模式下将19.6mN的载荷施加到样品上，以5℃/分钟的加热速率对放置样品的区域进行升温，以0.5秒的间隔测量样品的长度变化情况。破膜温度定义为样品膜破裂时的温度，一般在大约150℃-200℃的区间。
与现有技术相比，本发明产生如下有益效果：
1、本发明的聚烯烃多层微多孔膜具有低闭孔温度、高破膜温度、低的热收缩性和高的耐穿刺性能，质量稳定；
2、本发明的聚烯烃多层微多孔膜的制备方法工艺简单、制得的产品孔径均匀、质量稳定。
具体实施方式
下面通过具体实施例子对本发明作进一步详细描述以便清楚本发明所要保护的技术方案。
实施例1
使用高密度聚乙烯HDPE(Mw＝3.0×105，熔点133℃)、线性低密度聚乙烯LLDPE(Mw＝2.0×105，熔点120℃)作为制备中间层的聚乙烯原料，将22份重量的HDPE和3份的LLDPE加入双螺杆挤出机，再将75份重量的煤油通过侧向喂料口加入到双螺杆挤出机(长径比48)中，在220℃下熔融并混合均匀形成聚乙烯溶液，从三层模头的芯层挤出，厚度400μm。
将聚丙烯PP(Mw＝1.2×106，熔点166℃)和超高分子量聚乙烯UHMWPE(Mw＝1.0×106，熔点136℃)作为制备表面层的原料，将12份重量的PP和8份重量的UHMWPE加入双螺杆挤出机，再将80份重量的煤油通过侧向喂料口加入到双螺杆挤出机(长径比48)中，220℃下熔融并混合形成均匀溶液，从三层模头的两个表层挤出，厚度分别为400μm。
通过三层模头挤出的厚膜片以40℃～50℃/min的冷却速率通过冷水辊冷却至室温，制得厚度约为800μm的凝胶状厚片膜，膜片接着在130℃下双向拉伸6×5倍，拉伸后的薄膜通过盛有己烷洗涤槽洗涤、然后干燥并在130℃下热定型60s，得到20μm的三层微孔基膜。该膜的性能见表1。
实施例2
与实施例1不同之处在于，表面层选用分子量为2.1×106的超高分子量聚乙烯，其余与实施例1相同。隔膜的性能见表1。
实施例3
与实施例1不同之处在于，表面层选用分子量为5.0×106的超高分子量聚乙烯，其余与实施例1相同。隔膜的性能见表1。
实施例4
与实施例1不同之处在于，中间层的聚乙烯的分子量为6×105，表面层为16份重量的PP和4份重量的UHMWPE，其余与实施例1相同。隔膜的性能见表1。
实施例5
与实施例1不同之处在于，中间层的聚乙烯的分子量为1×105，表面层为19份重量的PP和1份重量的UHMWPE，表面层的聚乙烯的分子量为5×105，其余与实施例1相同。隔膜的性能见表1。
[表1]
Figure BDA0000112704570000071
Figure BDA0000112704570000081

Claims (1)

1.一种聚烯烃多层微多孔膜，其包括三层的聚烯烃微多孔膜，包括一层中间层和两层表面层，其特征在于：
所述中间层为聚乙烯微多孔膜，中间层采用分子量为3×105的高密度聚乙烯和分子量为2×105线性低密度聚乙烯的混合物制成，所述高密度聚乙烯以重量份计为22份，所述线性低密度聚乙烯以重量份计为3份，所述高密度聚乙烯的熔点为133℃，所述线性低密度聚乙烯的熔点为120℃；
所述表面层由聚丙烯与具有超高分子量的聚乙烯组成的微多孔膜，所述表面层中的采用分子量为1.2×106的聚丙烯和分子量为5.0×106超高分子量聚乙烯的混合物制成，所述聚丙烯以重量份计为12份，所述超高分子量聚乙烯以重量份计为8份，所述高密度聚丙烯的熔点为166℃，所述超高分子量聚乙烯的熔点为136℃；
所述聚烯烃多层微多孔膜的厚度为20μm；
所述聚烯烃为多孔膜由包括如下步骤的方法制得：
A、制备局乙烯溶液：将所述的高密度聚乙烯和线性低密度聚乙烯的混合物加入双螺杆挤出机，然后将重量份计75份的煤油通过双螺杆挤出机的侧向喂料口加入到双螺杆挤出机，在220℃的温度下熔融混合、制成聚乙烯溶液，所述双螺杆挤出机的长径比为48；
B、制备聚合物溶液：将所述的聚丙烯与超高分子量聚乙烯的混合物加入双螺杆挤出机，然后将以重量份计为80份的煤油通过双螺杆挤出机的侧向喂料口加入到双螺杆挤出机，在双螺杆挤出机中在220℃的温度下熔融混合、制成聚合物溶液，所述双螺杆挤出机的长径比为48；
c、共挤：将经过A步骤制得的聚乙烯溶液和经B步骤制得的聚合物溶液通过三层模头汇合在一起从同一模口挤出，其中：
将所述聚合物溶液分别从双螺杆挤出机的三层模头的两个表层挤出，制得两层厚度均为400μm的表面层；
将所述聚乙烯溶液从双螺杆挤出机的三层模头的芯层挤出，制得厚度为400μm的中间层；
接着，将上述挤出的中间层和两层表面层在冷水辊上以40℃～50℃/min的冷却速度冷却至室温制成厚度为800μm凝胶状厚片膜；
D、制膜：将经过C步骤制得的凝胶状厚片膜在130℃的温度下双向拉伸至6×5倍，制成薄膜；
E、萃取、定型：浆经过D步骤处理的薄膜在盛有己烷的洗涤槽洗涤，然后经干燥、在130℃热定型60s，制得产品。
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Address after: Chancheng District of Guangdong city in Foshan province 528000 quarter of Huayi Road No. 28, a two building 17 layer (residence declaration)

Patentee after: Foshan Jinhui Gao Ke photoelectric material Limited by Share Ltd.

Address before: 528000 Chancheng City, Foshan Province Light District, No. three road, No. 7, No.

Patentee before: FOSHAN JINHUI HIGH-TECH OPTOELECTRONIC MATERIAL Co.,Ltd.

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Effective date of registration: 20230109

Address after: 463000 industrial cluster area, Suiping County, Zhumadian City, Henan Province

Patentee after: HENAN HUIQIANG NEW ENERGY MATERIAL TECHNOLOGY Co.,Ltd.

Address before: 528000 Guangdong, Foshan, Chancheng, Ji Hua Road 28, a two 17 story (residence declaration)

Patentee before: Foshan Jinhui Gao Ke photoelectric material Limited by Share Ltd.

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