CN1242499C - 电池隔层-芯体的除去 - Google Patents
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Abstract
一种从电池组件中除去芯体的方法,它包括提供隔层的步骤,该隔层包括:有聚丙烯外表部分的微孔薄膜,聚丙烯中包含至少50ppm的硬脂酸金属盐,优选的为惰性(static)的硬脂酸钙,采用的微孔薄膜对芯体的除去力≤7100g。
Description
技术领域
本发明涉及电池的隔层,它具有改进了的芯体除去特性。
背景技术
在制造高能、轻量级的电池如锂二次电池时,电池的组件即夹在阳极带与阴极带间的隔离带绕在一个或多个芯体(或芯子或芯轴)上。该组件缠绕是将隔离带绷紧于芯体,然后将阳极带和阴极带移往到该芯体。缠绕完毕后,将该电池组件从芯体中除去(或抽去)。如抽去时该组件(即隔离带)卡住在芯体上,该组件“内层伸出(telescope)”而需报废。此种报废增加了电池制造的成本。因此电池制造商要求隔离带具有改进了的芯体除去特性,即该电池组件从芯体除去时隔层应不卡住在芯体上。
人们已作了一些努力来解决上述的芯体除去问题。1998年4月28日公布的日本公开10-110052使用对微孔膜表面作组织化处理来改善芯体的除去。优选由选自氟树脂和硅树脂中的至少一种树脂组成的有机树脂的球状粒子突出于膜表面,这种组织处理的表面减小了摩擦阻力。1998年5月26日公布的日本公开10-139918则使用润滑剂涂覆在微孔膜的表面来改善芯体的除去。可使用浸涂或滚涂来实施这种涂覆。润滑剂包括:蜡(如链烷烃蜡、微晶蜡、低分子量的聚乙烯和其他烃类的蜡);脂肪酸酯(如硬脂酸甲酯、硬脂酸硬脂酸酯、硬脂酸单甘油酯);脂肪酰胺(如硬脂酰胺、棕榈酰胺、亚甲基双硬脂酰胺),及它们的组合。在1998年7月28日公布的日本公开10-195215中,微孔膜的表面部分比其中间部分有更大的聚乙烯对聚丙烯的比值,该膜的表面部分有改进了的芯体除去特性。2000年9月13日公布的美国申请系列号09/661,519为了改善芯体的除去而对芯体的表面作了修饰。表面修饰包括对芯体表面作组织化(粗化)处理和/或凹槽化处理。
硬脂酸钙在聚烯烃树脂中作为一种添加剂使用是熟知的。可参见:《塑料工程手册》,Chapman & Hall出版,纽约市,NY,(1991),P.645。在这里要指出的是硬脂酸钙在聚烯烃中是作为“助催化剂”(tie upcatalyst)使用,润滑剂是用来提高树脂的加工性能,“有效的润滑剂对最终产品的特性没有不良影响”(即它们是惰性的)。例如,600ppm硬脂酸钙加入到聚丙烯中是起酸清除剂的作用。可参见Witco的
添加剂产 品指南,聚合物添加剂,烯烃/苯乙烯,P.2。硬脂酸钙也可作为润滑剂来改善聚烯烃树脂的流动特性。Witco,同上,P.2。在制造电池隔层如CELGARD2400,单层聚丙烯隔层,和CELGARD2300,多层的隔层,中已使用了含硬脂酸钙的聚丙烯树脂。
尽管已作了所述的工作,仍有必要改善这些隔层芯体的除去特性。
发明内容
一种从电池组件中除去芯体的方法,它包括提供隔层的步骤,所述隔层包括:
有聚丙烯外表部分的微孔薄膜,聚丙烯中至少含有50ppm硬脂酸的金属盐,和所采用的微孔薄膜对芯体的除去力≤7100g。
具体实施方式
此处使用的微孔薄膜是有贯通膜的许多微孔。微孔的平均孔径在0.005至10μm,优选0.01至5μm,最好优选在0.05至2μm。微孔薄膜也有Gurley(ASTM D726B)5至100秒,优选10-60秒。这些薄膜最好是“断路的薄膜”,也就是当发生如内部短路引起电池的温度急剧增高时,它们有停止阳极和阴极间离子流的能力。微孔薄膜有如本领域人员熟知的单层的薄膜或多层的薄膜。优选的多层结构为聚丙烯/聚乙烯/聚丙烯的结构(PP/PE/PP)。优选的单层薄膜是用聚丙烯制作的。薄膜的外表部分(一个新造的词语,它指的是单层薄膜或多层薄膜的表面)优选用聚丙烯,聚丙烯则优选等规的聚丙烯均聚物。这种聚丙烯的熔融流动指数(MFI)在1至4,优选1.2至1.7。该聚丙烯的密度在0.90至0.91g/cm3。这些薄膜优选使用挤出、渐冷、拉伸的方法制备(a/k/a“干拉伸”或Celgara法),但是也可以使用其它技术如“溶剂提取”制备。可见:Kesting,R.,合成的聚合物薄膜,John Wiley父子出版社,纽约市,NY(1985),在此列出供作参考。
现已确定在聚丙烯薄膜的外表部分含有硬脂酸金属盐并优选至少含有50ppm的硬脂酸金属盐时,它可以改善隔层的芯体除去特性。优选的硬脂酸金属盐是硬脂酸钙。最好是硬脂酸钙在聚丙烯中至少含有50ppm,可优选50-3000ppm,最好优选300g至600ppm。硬脂酸钙含量用感应耦合等离子体(ICP)分析进行测定。为得到改善芯体除去特性所需的硬脂酸金属盐最小量定为它的下限量。硬脂酸金属盐可从隔层中溶解出来进入电解液并由此对电解液的电化学性质产生不良影响,而当这种危险增大前所容许的硬脂酸金属盐的最大量则定为它加入的上限量。此种硬脂酸钙可从Greenwich,CT的Witco公司购得,它的商品名为“硬脂酸钙Regular”。
本发明将参照下面的实例作进一步说明。
可用以下的方法测量“芯体的除去力(g)”来定量描述芯体的除去特性。
可用电池缠绕机把隔层绕在芯体(芯子或芯轴)上。芯体为一有平滑的外表面、直径为4毫米(0.16英寸)的两块圆筒状芯轴。每块的横截面呈半圆形。以下所讨论的隔层是紧绷在该芯体上。对隔层的初始力(切向)为0.5kgf,以后以24秒254毫米(10英寸)的速率将隔层缠绕。缠绕是用一台张力辊将隔层绷紧在芯体上。张力辊包括位于隔层进料对面的、直径15.9mm(5/8″)的滚筒,施加105帕(1巴)大气压(当工作时)的19.1mm(3/4″)气缸和将滚筒与气缸相连接的6.4mm(1/4″)连杆。
隔层是由两块供试验的30mm(宽)×254mm(10″)薄膜所构成的。用5个隔层作试验,将试验结果平均,取平均值为试验的报告值。每块薄膜以25.4mm(1″)彼此重叠在缠绕机的隔层进料辊上拼接。在隔层的空端即拼接端的末端,用墨水打下12.7mm(1/2″)和177.8mm(7″)的标记。12.7mm(1/2″)标记端与芯体远离边(即邻近张力辊的那一边)对齐,这时隔层附在芯体的片层间开始用张力辊进行缠绕。当标记177.8mm(7″)离缠绕了的胶膜卷筒(jellyroll)(绕在芯体上的隔层)约为12.7mm(1/2″)时,在该标记处将膜隔切断,膜的空端用一块胶布(25.4mm(1″)宽,177.8mm(1/2″)重叠)贴紧于胶膜卷筒上。把该胶膜卷筒(即绕有隔层的芯体)从缠绕机上移走。一个可接受的胶膜卷筒应无皱纹、无内层伸出。
在带有测力计(load cell)(501bs×0.021b;Chatillon DFGS50)的抗张强度测定仪(即Chatillon公司的Chatillon TCD 500-MS型,Greensboro,NC)上放置胶膜卷筒。应变率是每分钟2.5英寸,以每秒100点的速率记录来自测力计的数据。以记录的力的峰值作为所报告的芯体除去力。
Gurley是按ASTM-D726(B)标准测量的。按名称为“纸和纸板的摩擦系数测量方法”的JIS P8147标准测量静态的COF(摩擦系数)。
实例
在表1中,样品C1-C2和1-2是单层的聚丙烯微孔薄膜,C1与C2是以商品名CELGARD2400市售的薄膜(现有技术,PA)。样品1与2是本发明的示例产品。这些样品每个通过圆形模头在200℃挤出,在150℃带有6%的拉伸下渐冷,和拉伸,即16-18%的冷拉伸和就表中所示的量带有松驰的热拉伸。
表1
C1(PA) C2(PA) 1 2
树脂 PP PP PP PP
MFI 1.2 1.2 1.2 1.2
总厚度,μm(mil) 25(1) 25(1) 25(1) 25(1)
Gurley,10cc/sec 24 24 24 24
孔隙率,% 40 40 40 40
总拉伸,% 100 100 100 100
硬脂酸钙,ppm 340 <1 250 1545
芯体除去力,g 6500 7200 6700 6600
静态平均COF 0.36 0.46 0.42 0.36
在表2中,样品C3,C4和3是多层(PP/PE/PP)微孔薄膜。C3与C4分别为CELGARD2300与CELGARDE162市售产品,样品3是本发明的示例产品。所有薄层PP在224℃用圆形模头挤出,所有的三层膜渐冷(125℃),并在11%拉伸下结合(133℃)。然后该膜作20-25%冷拉伸后热拉伸和松驰,表2示出了总拉伸量。
表2
C3(PA) C4(PA) 3
树脂 PP PP PP
MFI 1.2 1.2 1.2
总厚度,μm(mil) 25(1) 25(1) 25(1)
PP层厚度,μm(mil) 9(0.36) 9(0.36) 9(0.36)
Gurley,10cc/sec 24 24 24
孔隙率,% 40 40 40
总拉伸,% 109 109 109
硬脂酸钙,ppm 492 <1 584
芯体除去力,g 6900 7300 6100
静态平均COF 0.56 0.58
在表3中,样品C5和4是多层(PP/PE/PP)微孔薄膜。C5是CELGARD2320市售产品(现有技术(PA))。样品4是本发明的示例产品。所有薄层PP在224℃用圆形模头挤出。所有三层膜渐冷(125℃),并在11%拉伸下结合(133℃)。然后该膜在20-25%拉伸下冷拉伸后热拉伸和松驰,总拉伸示于表3。
表3
C5(PA) 4
树脂 PP PP
MFI 1.2 1.2
总厚度,μm(mil) 19.5(0.78) 19.5(0.78)
PP层厚度,μm(mil) 6(0.24) 6(0.24)
Gurley,10cc/sec 20 20
孔隙率,% 43 43
总拉伸,% 122 122
硬脂酸钙,ppm <1 428
芯体除去力,g 8300 6900
静态平均COF 0.41 0.46
在不违背本发明的精神与主要特性的情况下,本发明也可在其它形式下实施。相应地它的实施应参照所附的专利权利要求而不是按本发明范围所作的上述细述。
Claims (20)
1.一种从电池组件中除去芯体的方法,它包括提供隔层的步骤,所述隔层包括:
有聚丙烯外表部分的微孔薄膜,聚丙烯中至少含有250ppm硬脂酸钙。
2.权利要求1的从电池组件中除去芯体的方法,其中在聚丙烯中有250至3000ppm硬脂酸钙。
3.权利要求1的从电池组件中除去芯体的方法,其中微孔薄膜还含有贯通膜的多个微孔,所述的微孔的平均孔径在0.05至10μm,所述膜的Gurley为5至100秒。
4.权利要求1的从电池组件中除去芯体的方法,其中膜还包括有聚丙烯/聚乙烯/聚丙烯结构的多层膜。
5.权利要求4的从电池组件中除去芯体的方法,所述薄膜是断路隔层。
6.权利要求1的从电池组件中除去芯体的方法,其中的聚丙烯中含有熔融流动指数为1至4的聚丙烯。
7.权利要求6的从电池组件中除去芯体的方法,其中的聚丙烯是熔融流动指数为1.2至1.7的聚丙烯。
8.一种从电池组件中除去芯体的方法,它包括提供隔层的步骤,所述隔层包括:
有聚丙烯外表部分的微孔薄膜,聚丙烯中至少含有250ppm硬脂酸金属盐;膜的厚度≤25微米;和芯体的除去力≤7100g。
9.权利要求8的从电池组件中除去芯体的方法,其中的硬脂酸金属盐是硬脂酸钙。
10.权利要求9的从电池组件中除去芯体的方法,其中硬脂酸钙在聚丙烯中的含量在250至3000ppm。
11.权利要求9的从电池组件中除去芯体的方法,其中硬脂酸钙在聚丙烯中的含量在300至600ppm。
12.权利要求8的从电池组件中除去芯体的方法,其中微孔薄膜还包含有贯通膜的多个微孔,所述的微孔平均孔径为0.05至10微米,和所述薄膜的Gurley为5至100秒。
13.权利要求8的从电池组件中除去芯体的方法,其中薄膜还包括有聚丙烯-聚乙烯-聚丙烯结构的多层薄膜。
14.权利要求13的从电池组件中除去芯体的方法,所述薄膜是断路隔层。
15.权利要求8的从电池组件中除去芯体的方法,其中的聚丙烯含有熔融流动指数在1至4的聚丙烯。
16.权利要求15的从电池组件中除去芯体的方法,其中的聚丙烯是熔融流动指数在1.2至1.7的聚丙烯。
17.一种具有改进芯体除去特性的电池隔层,它包括:
在聚丙烯的表面部分并且该部分至少含有250ppm硬脂酸金属盐的微孔薄膜。
18.权利要求17的电池隔层,其中所述的硬脂酸金属盐是250至3000ppm的硬脂酸钙。
19.权利要求17的电池隔层,其中所述的聚丙烯有1至4的熔融流动指数。
20.权利要求17的电池隔层,它具有的芯体除去力≤7100g。
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US09/976,982 US6692867B2 (en) | 2001-10-12 | 2001-10-12 | Battery separator-pin removal |
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EP (1) | EP1302992A2 (zh) |
JP (1) | JP2003157824A (zh) |
KR (1) | KR100454695B1 (zh) |
CN (1) | CN1242499C (zh) |
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CA2397465A1 (en) | 2003-04-12 |
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