CN1088543C - 断路、三层蓄电池隔板 - Google Patents

断路、三层蓄电池隔板 Download PDF

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CN1088543C
CN1088543C CN95120899A CN95120899A CN1088543C CN 1088543 C CN1088543 C CN 1088543C CN 95120899 A CN95120899 A CN 95120899A CN 95120899 A CN95120899 A CN 95120899A CN 1088543 C CN1088543 C CN 1088543C
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俞维清
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Abstract

本发明步及一种断路、三层蓄电池隔板。该隔板有第一和第二微孔隔膜，它们夹入第二微孔隔膜。第一和第三隔膜比第二隔膜具备较大的刺穿强度。第二隔膜具有比第一或第三隔膜都低的熔融温度。

Description

断路、三层蓄电池隔板
本发明涉及一种断路蓄电池隔板。
断路蓄电池隔板是已知的。例如，参见美国专利4650730，4731304，5240655，5281491和日本公开6-20671，上述的每一篇都在此引入作为参考。
在蓄电池中，阴极和阳极彼此由一隔板分隔开。如今“锂电池”非常流行，因为它们能产生高能输出。锂电池市场可被分为两组，即“原生”锂电池和“二次”锂电池组。原生锂电池是一次应用蓄电池，而二次锂电池组是可再充电的蓄电池。与二次锂电池组相关的问题是其短路电势。此短路可表现为其本身迅速放热。此迅速放热可造成电池爆炸。因此发展了断路蓄电池隔板。
断路蓄电池隔板一般包括两个聚合物的不同和并列的微孔隔膜。一个微孔隔膜是由于其相当低的熔点被选取，另一个则是由于其相对强度被选取。例如，低熔点隔膜可以是聚乙烯材料而强度隔膜可以是聚丙烯材料。聚乙烯微孔隔膜的熔点大约是130-135℃，这是足够低的温度，致使锂电池万一短路，所产生的热将熔融此聚乙烯而断路，或填充到隔板的细孔内，并因此而停止或阻止可能发生的短路。聚丙烯隔膜具有大体上较高的熔点，约160℃，它对隔板提供强度因此即使在短路情况下它也可保持隔板的完整性。
在美国专利4650730，4731304，5240655和5281491以及日本公开6-20671中揭示了上述类型的断路蓄电池隔板。在美国专利4650730和4731304的例子中揭示了厚度为3-4密耳的双层隔板。在日本公开6-20671中，断路双层蓄电池隔板的厚度为大约1至2密耳。
在美国专利5240655和5281491中揭示了多层隔板。在美国专利5240655的例2和3中，揭示了一种聚乙烯-乙烯丁烯共聚物-聚乙烯三层隔板。在美国专利5281491的例4中，揭示了一种聚乙烯-乙烯丁烯共聚物-聚乙烯三层隔板。上述每种隔板都是通过共挤出、脱模、拉伸工艺而制备的隔板。
在设计上述类型的新断路蓄电池隔板时，除了断路特性以外还有几个参数是重要的。它们包括薄度，刺穿强度和撕裂强度。在制造蓄电池时，重要的是有极薄的隔板，因此跨越隔板的电阻以及蓄电池的尺寸可被减小。在蓄电池制造中，特别是在“胶体辊”类型蓄电池的制造中，良好的刺穿强度是重要的，因为阳极和阳极的表面可足够地粗糙以致在制造过程中它们可能刺破这些极薄的隔板。在蓄电池制造中良好的撕裂强度也是重要的因为它可防止隔板的分层。因此需要生产一种极薄的断路蓄电池隔板，它具有足够的刺穿强度和撕裂强度来经受蓄电池生产的严格性。
在二次锂电池组的生产中良好的刺穿强度具有特别的重要性。在二次锂电池组中所用的阴极和阳极一般具有粗糙的表面。这些粗糙表面提出了一个特殊的需要考虑的制造问题，因为在蓄电池的组装过程中它们可能损坏该薄的隔板。双层蓄电池隔板有一断路层和一强度层，在制造过程中，它们极有可能被粗糙的电极表面损坏断路层(它比强度层更脆弱)。因此在制造蓄电池，例如二次锂电池组中，蓄电池隔板需要尤其是承受侧面粗糙的电极。
本发明涉及断路、三层蓄电池隔板。此隔板有第一和第三微孔隔膜，它们夹入第二微孔隔膜。第一和第三隔膜比第二隔膜刺穿强度高。第二隔膜比第一或第三隔膜的熔融温度都低。第一和第三隔膜优选由聚丙烯制取。第二隔膜优选由聚乙烯制取。
本发明的目的在于提供能够更好地承受蓄电池生产的苛刻条件的蓄电池隔板。
本发明的目的还在于提供其刺穿强度大于或等于450克的蓄电池隔板。
本发明的目的还在于提供厚度小于0.5密尔的微孔隔膜的制备方法。
为了解释本发明，在图中显示了本发明的不同的优选方式；然而应当理解，本发明并不受限于所展示的准确配置和手段。
图1是一三层蓄电池隔板的断路蓄电池能力(以电阻、欧姆测量)作为温度(℃)的函数的示意图。
图2是三层结构位置和展开的示意图。
通过以下的详细叙述和非限制性例子对本发明进一步详细叙述。
按照本发明的一个具体实施方案，本发明提供一种断路、三层蓄电池隔板，其中包括第一和第三微孔聚丙烯隔膜和被夹在其中的微孔聚乙烯隔膜，所述隔板的厚度小于3密尔，刺穿强度大于或等于450克，撕裂强度大于或等于每英寸4克。
按照本发明的优选实施方案，本发明的蓄电池隔板包括厚度范围为0.5-1.5密耳的隔板，优选厚度为1密耳的隔板。
按照本发明的优选实施方案，本发明的蓄电池隔板的刺穿强度大于或等于480克，所述撕裂强度优选大于或等于每英寸6克。
按照本发明的一个具体实施方案，本发明提供一种包括上述断路、三层蓄电池隔板的蓄电池。
按照本发明的另一个具体实施方案，本发明提供具有厚度小于0.5密耳的微孔隔膜的制备方法，其中包括以下步骤：
当同环间隙范围为5/64～10/64英寸时，在采用压力为0.6-3.0英寸水柱的气体进行急冷的同时挤出一型坯，当所述隔膜为聚丙烯时挤出模头的温度范围为210～224℃；
将该型坯本身叠并形成含有两层的平片；
退火该平片；
拉伸该平片，其中当所述隔膜为聚丙烯时退火/拉伸温度范围为120～125℃，当所述隔膜为聚乙烯时，退火/拉伸温度范围为110℃；和
收卷该平片，二层之间的粘合力小于每英寸8克。
按照上述方法，对于制备厚度小于或等于0.33密耳的微孔隔膜，其中粘合力小于每英寸5克。
按照本发明的另一个具体实施方案，本发明提供一种制造三层断路蓄电池隔板的方法，其中包括以下步骤：
提供含有两层微孔聚丙烯隔膜的第一和第三平片，该隔膜是根据权利要求7的方法制备的；
提供含有两层微孔聚乙烯隔膜的第二平片，该隔膜是根据权利要求7的方法制备的；
展开第一和第三微孔聚丙烯隔膜平片；
展开第二聚乙烯微孔隔膜平片；
把各层层合形成聚丙烯-聚乙烯-聚丙烯结构；
粘结该结构形成三层隔板；和收卷该隔板。
按照上述方法的一种变化形式，其中粘结过程包括压延或用粘合剂粘合或焊接。
此处所用的断路蓄电池隔板是指这样的蓄电池隔板，根据特殊情况，例如快速放出热，此隔板具有中断离子迁移穿越隔板的能力。在图1中图形图解了断路蓄电池隔板的功能。断路能力用电阻(欧姆)来表示，放热用温度(℃)来表示。当温度在初始范围增加时，电阻变化很小。然而当温度达到断路层的熔融温度时，电阻值形成峰值。电阻达到峰值之后直到温度达到强度层的熔融温度，电阻值为平稳状态。绘制图1曲线所用的数据是根据本发明所制的三层断路蓄电池隔板经测试而得到的。此三层隔板的结构为聚丙烯(PP)-聚乙烯(PE)-聚丙烯(PP)。有关断路蓄电池隔板进一步的资料可从以下文献中得到：美国专利4640730，4731304，52240655，5281491，日本公开6-20671，美国专利申请号08/341239，申请日1994年11月17日，题目为“制造交叉层微孔隔膜蓄电池隔板的方法，以及由此而制成的蓄电池隔板”，和美国专利申请号08/348630，申请日1994年12月2日，题目为“断路、双层蓄电池隔板”，它们每一篇都被引用在此作为参考。
本发明的断路蓄电池隔板至少有三层。它们的每一层当然都是微孔的并且最好是独立的微孔隔膜。(例如参考Kesting.R.E.合成聚合物隔膜，第二版(Synthetic Polymeric Membranes)Johm Wiley&Sons，New York City.NY(1985)在8.2段落与第7章Ibid相比较，此参考文献在此引入作为参考)。最外层提供强度，尤其是耐刺穿强度，例如被粗糙的电极表面刺穿。此强度质量或许可用刺穿强度(下面定义)定量表示。在这些最外层之间的一层提供断路特性。最好是最外层的穿刺强度比内部断路层的穿刺强度相对大一些，内部断路层的熔融温度比最外强度层的熔融温度相对低一些。在三层断路蓄电池隔极的优选实施例中，最外层的强度层夹入内部的断路层。
以上所述最外层的强度性能是该层的本质功能，但不必是唯一的功能，这可以简化蓄电池的生产，即对隔板提供较高的穿刺强度，以及万一短路时维持该隔板的完整性。优选在锂蓄电池中，由某种材料提供强度性能，该材料在大约或高于最低熔化电极(例如锂材料)的熔融温度的温度熔融。这种材料的一个例子是聚烯烃，例如聚丙烯或实质上含有聚丙烯或聚丙烯共聚物的共混料。
以上所述内层的断路性能是该层的本质功能，但不必是唯一的功能，该层在万一短路的情况下能闭合隔板的微孔。这一般意味着在某温度该断路层熔融，填塞隔板的细孔，并由此通过阻止离子迁移跨越该隔板而结束短路。最好是，在锂蓄电池中由这样一种材料来提供断路性能，该材料在比最低熔化电极的熔化温度(例如，锂材料，锂的熔点大约是180℃)低至少20℃的温度熔融。这种材料的一例是聚乙烯或实质上含有聚乙烯或实质上包括大于110℃熔融温度的聚乙烯的共聚物的共混料。
这些隔板的厚度小于3密耳(大约75微米)。这些隔板的厚度的优选范围在0.5密耳(约12微米)和1.5密耳(约38微米)之间。最优选的是，该隔板的厚度为大约1密耳(约25微米)。该隔板的总厚度主要是各层的总和，这些各个层最好具有大体相同的厚度，测量细节在下面规定。
刺穿强度优选应大于或等于450克，最优选的刺穿强度应大于或等于480克。这些测量是在平均孔隙率为35％条件下进行的。测量的细节在下面规定。
撕裂强度优选大于或等于4克/英寸(1克/厘米)。最优选的是，撕裂强度应大于或等于6克/英寸(1.5克/厘米)。测量细节在下面规定。
用以制造本发明的隔板的方法概括地包括制取第一和第三微孔隔膜，制取第二微孔隔膜，把第一、第二和第三隔膜粘结在一起。关于制取隔膜的优选方法，该工艺要求如下步骤：挤出聚合物形成一片材，退火该片材，然后拉伸该已退火的片材。制取这些片材，特别是聚乙烯或聚丙烯的特殊方法将参考制取厚度大于1密耳的隔膜的方法来讨论。作为非限制性例子，以下的参考文献(它们每一篇都在此引入作为参考)都举例说明了制取厚度大于1密耳的隔膜的现有技术状态：美国专利3426754，3558764，3679538，3801404，3801692，3843761，3853601，4138459，4539256，4726989和4994335上述的每一篇文献均引入作为参考。由于这些方法的知识已被接受，因此在以下叙述本发明制取薄隔膜的工艺时只解释现有技术制取标准薄膜(厚度大于1密耳)的方法与本发明制取薄膜(厚度小于约1/2密耳)的方法之间的差别。
以下所讨论的关于挤出，退火和拉伸的差别基于27吋模头的模头构型，该模头配置有70密耳的芯棒间隙。如果模头的构型改变，则该差别也将改变。例如，如使用6英寸的模头，则标准膜工艺和薄的膜工艺之间的模头温度差别就非常小。不管模头构型怎样，薄的膜需要较少的急冷空气。
关于挤出条件，标准膜工艺一般比薄的膜工艺需要较强的急冷空气条件和较低的挤出温度。例如，对于标准膜工艺的相关急冷条件包括：空气压力大约6″H2O，同环间隙在10/64至15/64英寸范围内；同环高度1至2英寸；另一方面，对于薄的膜工艺的相关急冷条件包括：空气压力大约0.6至3.0英寸H2O，同环间隙在5/64至10/64英寸范围内，同环高度约1至2英寸。对于标准膜工艺的相关挤出条件(例如使用Exxon′s Escorene pp4292树脂)包括：模头温度在191-198℃范围，轨筒温度为200-205℃；另一方面，对于薄的膜工艺的相关挤出条件(使用相同的材料)包括：模头温度在210℃(对于0.5密耳的最终产品)至224℃(对于0.33密耳的最终产品)范围，机筒温度为210℃。
关于退火和拉伸条件，中心层粘合力(作为撕裂强度测量)必须小于标准工艺的中心层粘合力，因此当各层被分层时它们并不裂缝(即撕开)。耐劈裂的能力正比于该层的厚度。这样，如果各层附着在一起(由于粘合力)，则附着性大于耐劈裂性，因此如无裂缝各层不能被分离(分层)，例如厚度大约为1密耳的层的粘合力应小于大约15克/英寸，而对于0.5密耳的层，粘合力应小于大约8克/吋，对于0.33密耳的层，则要小于大约5克/吋。为了降低粘合力数值，对于本发明的工艺，退火和拉伸温度均低于标准工艺的退火和拉伸温度。例如，对于聚丙烯膜退火和拉伸温度在120-125℃(本发明工艺)范围内，相对于140-150℃(标准工艺)的范围，对于聚乙烯膜约为110℃(本发明工艺)相对于大约1150℃(标准工艺)。
为了防止形成皱折，铺设修整过的2层膜直至形成三层隔板。膜的展开构型示于图2。在图2中，显示的是展开的和三层结构层系统10。系统10包括基极配置12和高架配置14。配置12和14除了高度以外(是为了有效地使用空间)是相同的，因此只详细讨论配置12。配置12包括三个放卷站16，18和20。站16和20支承着聚丙烯微孔隔膜辊(即一辊-2层)，站18支承着聚乙烯微孔隔膜辊(即一辊-2层)。这些隔膜(即或是PP或是PE隔膜)单层形式为大约1/3密耳那样薄，这种厚度的隔膜或膜易于皱折或卷边。为了避免皱折或卷边，将这些隔膜以2层的形式(大约2/3密耳厚)使用(尽可能多)。聚丙烯膜24和聚乙烯膜26从它们的辊上放卷，展开，在某些情况下还要受助于导辊22，然后再复合形成三层前体28。由系统10，可形成4个三层前体28。至少四个三层前体是优选的，由此可避免皱折问题并更有效地使用设备(经济原因)。为了加工经济至少两个三层前体是最低的优选数。前体28被转送至粘结站30(未示)。
关于把隔膜粘结在一起的优选方法，预料有几种粘合方法。概括地讲，这些粘结方法包括压延，用粘合剂粘合和焊接。粘合剂的应用可以包括空气雾化；凹板/丝网印刷；液压喷涂；和超声喷涂。粘合剂的选择以及粘合剂应用比率必须这样选择致使隔板的孔隙率不受到不利影响。焊接技术包括热焊接和超声焊接，不管是焊接程序还是焊接方式其能量都应这样选择，致使尤其是隔板的孔隙率不受到不利影响。最好是，粘结通过压延，用贴近的辊隙，在125-130℃温度范围，和在该温度的保留时间大约2-10分钟进行。
粘结后，将三层断路蓄电池隔板复卷用于制备蓄电池，尤其是二次锂电池组，就如现有技术所熟知的那样。
关于上述发明的进一步资料可从以下的非限制性例子中获得。在此处所涉及的测试方法在下面加以规定。测试方法Gurley ASTM-D726(B)
Gurley是用Gurley密度计(例如4120型)测量的空气流动阻力，Gurley是10毫升空气在1202英寸水柱压力下穿越1平方英寸产品所需要的时间(秒)。厚度方法：T4110m-83是在纸浆和纸工业技术协会赞助下开发的。厚度使用精密的千分尺来测定，该千分尺用1/2英寸直径圆形极靴在7PSI压力下接触样品。将穿过样品宽度所取的10个单独的千分尺读数取平均值。孔隙率  ASTM D-2873。密度ASTM D-792。刺穿强度  跨越已拉伸产品的宽度测量十次并取平均值。使用Mitech Stevens LFRA Texture Analyzer(织物分析仪)。针的横断面1.65毫米，半径0.5毫米。下降速度为2毫米/秒，偏移量为6毫米。该薄膜用带有11.3毫米中心孔的夹持装置紧紧卡住。被针刺穿的薄膜的位移(毫米)相对于被测试薄膜所产生的阻力(克力)被记录下来。最大的阻力值就是刺穿强度。撕裂强度撕裂强度是这样测量的，用一张力和压缩测试仪来测定要分开两个一英寸宽截面的粘结隔膜所需的力(克)。撕裂速率是6英寸/分钟。跨越该坯料测量三次取平均值。熔融指数  ASTM D1238；PE：190℃/2.16公斤；PP：230℃/2.16公斤。
以下述方式制备以上所揭示的断路三层蓄电池隔板：
所用聚丙烯和聚乙烯树脂被指定为以下表1和2中的树脂：
                          表1
                        聚丙烯(pp单聚物)
树脂     密度克/厘米3     熔融指数(克/10分钟) 供应厂商
A     EscorenePP4292     0.90     1.4     ExxonChemical
  B   Fina PP 3271     0.905     1.5   Fina oil&Chemical
  C   Fina PP 3281     0.905     1.1   Fina oil&Chemical
  D     EscorenePP4292(核化的)     0.90     1.4     ExxonChemical
  E     EscorenePP4372*     0.90     1.4     ExxonChemical
  F     EscorenePP3182     0.90     3.0     ExxonChemical
*含有防粘连剂
                        表2聚乙烯(HDPE)
    树脂 密度克/厘米3 熔融指数(克/10分钟) 供应厂商
  G     FinaHDPEGF7750     0.958     0.70   Fina oil &Chemical
  H   EscoreneHDZ107     0.964     0.30     ExxonChemical
挤出设备按以下表3中所指定的配置：
                  表3挤出机
    L/D比值   机筒尺寸 模头尺寸   模口  成型段长度   吹胀比
    E1     24     2.5″   12″或27″ 70密耳     3″     1
    E2     24     3.5″   12″或27″ 70密耳     3″     1
    E3     30     1.25″     6″ 70密耳     3″     1
树脂按表4中规定的条件挤出并按表4中规定的条件形成一简状前体薄膜(型坯)：
                              表4挤出条件
产品 树脂(见表1和2)    挤出机/摸头尺寸(见表3) 挤出机温度(℃)   熔融温度(℃)   摸头温度(℃)   风环高度(吋)   急冷气体压力(吋H2O)   风环开口(吋)     厚度(密耳)   线速度英尺/分钟
    P1     A     E3/6″     200   205   205     1″     1.5″     0.078″     0.38     42
    P2     C     E3/6″     205   215   215     1″     1.5″     0.078″     0.38     42
    P3     C     E2/27″     230   243   243     1″     1.2″     0.078″     0.38     47
    P4     A     E2/27″     210   224   224     1″     1.2″     0.078″     0.38     50
    P5     A     E2/12″     220   224   224     1″     1.2″     0.078″     0.38     50
    P6     B     E2/27″     210   224   224     1″     1.2″     0.078″     0.38     50
    E1     G     E1/27″     200   220   200     1″     1.0″     0.078″     0.38     60
    E2     H     E1/12″     180   199   185      1.25″     1.0″     0.094″     0.59     60
该前体薄膜以8层膜进行退火。这意味着由于该前体薄膜是作为充气管状物挤出的，当它们被压扁时，它们就形成2层薄膜。4个这样的2层膜卷拢在一起制成8层膜。退火条件在以下表5中规定：
                                 表5退火条件
产品(见表4) 退火温度(℃)   退火时间(分钟)   撕裂强度(克/吋)
    P1     136     16     -
    P2     140     16     -
    P3     120     16     -
    P4，P5     120     16     2
    P6     135     16     0
    E1     110     19     1
    E2     115     19     1
将该被退火的前体薄膜拉伸形成微孔隔膜。把已退火的前体薄膜作为16层膜拉伸(8卷所挤出的筒状前体2层膜)。用另一种方法，该已退火的前体薄膜可以作为8层膜或24层膜被拉伸。拉伸条件在以下的表6中规定：
                               表6拉伸条件
    产品(见表5) 冷拉伸温度(℃) 冷拉伸*   热拉伸温度(℃) 热拉伸u 热松驰温度(℃) 热松驰*1   厚度(密耳) Gurley(秒)
    P4，P5     25％     120℃     115％     120℃     40％     0.33     12
    P6     25％     135℃     115％     135℃     40％     0.33     10
    E1     40％     110℃     110％     110℃     50％     0.33     8
    E2     45％     115℃     105％     115℃     40％     0.5     11
*  拉伸/松驰的百分比是基于冷拉伸以前的原始长度。1  该松驰步骤表明该已拉伸的薄膜被允许收缩回来。
该微孔隔膜作为16层薄膜被展开至2层薄膜。该2层膜的边缘部分被修整，由此将该2层膜分离为单一的脱体层。该PP层被修整为比PE层宽0.5吋。
该三层前体通过在128℃压延，250尺/分钟线速度，和在粘结温度下保留时间大约5-10分钟而粘结在一起。
根据上述例子而制成的三层隔板具有以下表7中所显示的性能：
                         表7三层隔板的性能
产品 PP/PE/PP(见表6)   厚度(密耳) Gurley(秒)   刺穿强度(克)   粘合力(克/厘米)
    T1  P2/E1/P2     1.02     20     480     4.3
    T2  P4，P5/E1/P4，P5     1.01     29     480     -
    T3  P6/E1/P6     1.01     22     483     -
T4 P4，P5/E2/P4，P5 1.15 30 500 6.5
在表8中将三层蓄电池隔板的性能与其它蓄电池隔板进行比较(celgard-型单层PP；celgard-型单层PE，双层PP/PE(参见美国专利申请系列号08/348630，1994年12月2日申请)；和交叉层PE(参见美国专利申请系列号08/341239，1994年11月11日申请))；
                  表8三层(PP/PE/PP)与其它蓄电池隔板的比较
性能 单层PP 单层PE     双层PP/PE     交叉层PE/PE     三层PP/PE/PP
厚度(密耳)     1.0     1.0     1.0     1.0     1.0
孔隙率(％)     38     38     38     38     38
Gurley(秒)     25     25     25     25     25
断路温度(℃)     165     132     132     132     132
断路温度范围(℃)     -     20     35     20     35
刺穿强度(克)     380     290   490(PP)300(PE)     490     480
本发明也可表现为其它特殊形式，而不脱离其精神或基本特性，因此，审查范围应是对附加的权利要求，而不是前述作为简述本发明范围的详细说明。

Claims (10)

1.一种断路、三层蓄电池隔板，其中包括第一和第三微孔聚丙烯隔膜和被夹在其中的微孔聚乙烯隔膜，所述隔板的厚度小于3密耳，刺穿强度大于或等于450克，撕裂强度大于或等于每英寸4克。
2.权利要求1的蓄电池隔板，其中所述隔板的厚度范围为0.5-1.5密耳。
3.权利要求2的蓄电池隔板，其中所述隔板的厚度为1密耳。
4.权利要求1的蓄电池隔板，其中所述刺穿强度大于或等于480克。
5.权利要求1的蓄电池隔板，其中所述撕裂强度大于或等于每英寸6克。
6.一种包括权利要求1的隔板的蓄电池。
7.具有厚度小于0.5密耳的微孔隔膜的制备方法，其中包括以下步骤：
以同环间隙范围为5/64～10/64英寸，在采用压力为0.6-3.0英寸水柱的气体进行急冷的同时挤出一型坯，当所述隔膜为聚丙烯时挤出模头的温度范围为210～224℃；
将该型坯本身叠并形成含有两层的平片；
退火该平片；
拉伸该平片，其中当所述隔膜为聚丙烯时退火/拉伸温度范围为120～125℃，当所述隔膜为聚乙烯时，退火/拉伸温度范围为110℃；和
收卷该平片，二层之间的粘合力小于每英寸8克。
8.根据权利要求7的方法，对于制备厚度小于或等于0.33密耳的微孔隔膜，其中粘合力小于每英寸5克。
9.一种制造三层断路蓄电池隔板的方法，其中包括以下步骤：
提供含有两层微孔聚丙烯隔膜的第一和第三平片，该隔膜是根据权利要求7的方法制备的；
提供含有两层微孔聚乙烯隔膜的第二平片，该隔膜是根据权利要求7的方法制备的；
展开第一和第三微孔聚丙烯隔膜平片；
展开第二聚乙烯微孔隔膜平片；
把各层层合形成聚丙烯-聚乙烯-聚丙烯结构；
粘结该结构形成三层隔板；和收卷该隔板。
10.根据权利要求9的方法，其中粘结过程包括压延或用粘合剂粘合或焊接。
CN95120899A 1994-12-20 1995-12-19 断路、三层蓄电池隔板 Expired - Lifetime CN1088543C (zh)

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DE69512877D1 (de) 1999-11-25
KR960027005A (ko) 1996-07-22
EP0718901B1 (en) 1999-10-20
US5691077A (en) 1997-11-25
KR100388890B1 (ko) 2003-09-06
DE69525549T2 (de) 2002-08-29
CN1132946A (zh) 1996-10-09
US6132654A (en) 2000-10-17
TW297171B (zh) 1997-02-01
EP0892448A2 (en) 1999-01-20
US6057060A (en) 2000-05-02
DE69525549D1 (de) 2002-03-28
JP3960437B2 (ja) 2007-08-15
JPH08222197A (ja) 1996-08-30
EP0718901A1 (en) 1996-06-26
EP0892448A3 (en) 1999-03-10
EP0892448B1 (en) 2002-02-20

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