CN1226473C - 含有聚氧化烯纤维的无纺布作为电池隔片的应用 - Google Patents

含有聚氧化烯纤维的无纺布作为电池隔片的应用 Download PDF

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CN1226473C
CN1226473C CNB02120652XA CN02120652A CN1226473C CN 1226473 C CN1226473 C CN 1226473C CN B02120652X A CNB02120652X A CN B02120652XA CN 02120652 A CN02120652 A CN 02120652A CN 1226473 C CN1226473 C CN 1226473C
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P·克里泽
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Carl Freudenberg KG
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Abstract

本发明描述了一种含有聚氧化烯纤维的无纺布。根据已知的无纺布制备方法可制备得到这种无纺布，这种无纺布特别地可用作为电池的隔片。

Description

含有聚氧化烯纤维的无纺布 作为电池隔片的应用
                       发明领域
本发明涉及到含有聚氧化烯纤维的无纺布及其制备和应用，特别是用来制备碱性充电电池中的隔片。
                       背景技术
聚缩醛共聚物(也称作“聚甲醛”或“POM”)是一种从60年代以来的商品聚合物。这些聚合物的例子有产品“Hostaform”(Ticona GmbH)，“Ultraform”(BASF AG)或“Sniatal”(Rhodia)。这种材料主要作为注塑材料例如用在汽车工业中。它的例如耐碱性介质和有机溶剂的化学性能是优越的。
由这种材料制备单丝已经有描述(参见例如US-A-4,060,582；GB-A-1,439,886；和FR-A-1,473,682)。
人们也已获知由这种材料制纤维的可能性(参见例如JP-A-51/26,322；FR-A-1,584,083；DE-A-1,947,430；GB-A-1,449,581)。
含有这种材料制成的纤维的无纺布在文献资料中迄今为至还没有描述过。
在有化学腐蚀性物质的环境中，例如在电池中，传统的无纺布是不容易被采用的。在碱性充电电池中无纺布用作为隔片。
隔片在蓄电池中分离开二个不同的带电电极，这样就阻止了内部短路。对于隔片材料有如下的一系列要求：耐电解液，耐氧化，较小的离子通过阻力，较高的电子通过阻力，通过电解液的持久可润湿性，对于电解液的高存储器容量，对于从电极溶解下来的粒子的阻挡能力，小的厚度公差和高的机械稳定性。
迄今为止碱性充电电池所应用的隔片材料必须克服二个难题。一方面这些隔片材料应能阻止电池的自放电或至少不支持这种自放电，另一方面这些隔片材料必须具有对于电解液一个持久的“基本”可润湿性能。
文献资料中认为碱性充电电池的自放电是氨引起的。氨不仅是作为电极活性材料的污染物存在，而且其还通过分解含氮的隔片材料(如聚酰胺基的隔片材料)而释放出来。
氨在阳极被氧化成亚硝酸盐或硝酸盐，这些亚硝酸盐或硝酸盐在阴极又被还原成氨，结果就形成了“放电-循环”(所谓的“硝酸盐-氨-往复变化”)。这种即使电池处于不工作状态下也发生的现象在镍-金属氢化物-电池中特别突出，在这种电池中由于在阴极中有氢-自由基存在而极大地加速了亚硝酸盐/硝酸盐的在其它时候缓慢的还原过程。这种自放电一直是镍-金属氢化物-电池的最大的问题。
在镍-镉蓄电池中也有自放电现象。
聚酰胺无纺布在强碱性电解液中出现明显的分解而释放出氨。所以它几乎只被用在镍-镉蓄电池中。
所以现在在镍-金属氢化物-电池中几乎都应用聚烯烃基的隔片。这种隔片对于电解液(30％的氢氧化钾；温度直至约70℃)是化学稳定的。然而由于其非极性的表面，所以它的可润湿性是非常差的。缺少可润湿性又要导致二个严重的问题。一个是在电池的生产过程中在装填电池时的起始可润湿性是差的。这导致了或者只能加入少量的电解液(这就限制了电池的容量)，或者要极大的延长生产时间(这使得生产过程变得昂贵)。另一个是由于缺少持久的可润湿性，电池在工作时是处于“干燥运转”，这就要导致电池出现故障而停止工作或缩短电池的寿命周期。
为了提高聚烯烃基隔片材料的极性，所以现在对这种隔片进行进一步的生产步骤，例如局部气相氟化或化学浸渍。
通过加入与氨化合的物质，如丙烯酸或硫酸可减少由上述的电极-活性材料的污染物引起的自放电，在此表面的活化种类起重要的作用。这二种方法是非常昂贵的，所以是高成本的，并且在后一种方法的情况下由于使用了高浓度的硫酸，从工作安全和环境角度看是一种不好的方法。
                        发明内容
根据本发明可制备出一种无纺布，该无纺布与聚酰胺比较具有高得多的耐化学腐蚀性化合物的腐蚀性能，例如在充电电池的强碱性电解液中的化合物，结果是产生显著较少的分解。此外还有，可能的分解产物不促进例如镍-金属氢化物电池的自放电。
POM由于在其分子中有氧原子所以相对于聚烯烃具有较高的“基本亲水性”，所以不用进行以后的用于特定用途的处理，如气相氟化。此外由于无纺布纤维材料的耐化学腐蚀性，所以可确保在应用过程不丧失基本亲水性，这在以后化学表面处理时原则上可发生的(例如在浸渍时，所涂上的物质与表面在化学上是无关的)。
未被整理了的或氟化了的隔片无纺布不具有生成氨的性能(滴定分析确定的所谓的“氨捕获”比率为每克隔片材料小于0.05×10-4摩尔氨)。与此相反，“非常好的”隔片材料显示出每克大约2-3×10-4摩尔氨。
此外现在发现，根据本发明的无纺布具有良好的值即每克0.5×10-4摩尔氨。这就是说，由于具有良好的氨化合能力使其可能不用进行整理或后处理。
本发明涉及到一种含有聚氧化烯，优选为聚甲醛的纤维的无纺布。
根据本发明的无纺布可由不同纤度范围的任意的纤维种类构成，例如0.5-5dtex的纤度。该无纺布除了长丝还可由短纤维构成或含有短纤维。
除了可采用均匀的纤维，也可采用不均匀的纤维或各种不同的纤维混合物，只要至少一种纤维由聚氧化烯构成或至少含有氧化烯(例如皮/芯纤维)。
根据本发明的无纺布可以任意一种已知方法，以湿法或干法制备，例如用纺粘无纺布方法，梳理法，熔吹法或湿无纺布方法。
根据本发明所采用的聚氧化烯是一种这样的聚合物，该聚合物具有化学式I的重复结构单元，
-(CnH2n-O)-    (I)
其中n为整数1-4，优选为1和/或2。
除了可采用聚氧化烯均聚合物也可采用含有化学式I的重复结构单元和由共聚单体派生出的重复结构单元的共聚物。
共聚物例如为含有化学式I的重复结构单元的聚氧化烯共聚物，其中n＝1(聚甲醛)和n＝2(聚氧乙烯)。这种POM共聚物是从三噁烷(n＝1)和二噁烷(n＝2)中衍生出来的。
典型的根据本发明的无纺布具有5-500g/m2的单位面积重量。
特别优选采用的无纺布具有5-150g/m2的较小的单位面积重量。
本发明的一个优选的实施形式涉及到由聚氧化烯纤维，特别是上述的优选的共聚合物与聚酰胺纤维联合的无纺布；或涉及到由聚氧化烯纤维，特别是上述的优选的共聚合物与聚烯烃联合的无纺布。另一些优选的聚合物是聚苯硫醚，聚砜和聚四氟乙烯，这些聚合物可以纤维形态与聚氧化烯纤维一起使用。
本发明的另一个优选的实施形式涉及到含有聚氧化烯纤维的无纺布，纤维用给予亲水性的或提高亲水性的化合物处理。这种无纺布通常比未处理过的具有提高了的基本亲水性。
对于这样的整理的例子是已知的。在此涉及到表面处理，例如氟化、化学浸渍，电晕-或等离子体处理，用不饱和的羧酸接枝或为磺化。这些方法用于进一步改善亲水性或用于减小自放电。
特别优选的是聚酰胺-和聚氧化烯纤维的联合。这种无纺布特别地能用作为镍-镉-电池的隔片。这种联合具有聚酰胺隔片的基本未衰减的高亲水性以及化学耐腐蚀性，这种性能可与聚酰胺/聚烯烃联合的性能相比较。
在同样优选的聚烯烃和聚氧化烯纤维的联合中也表明这种联合具有良好的氨化合能力，这就例如优选地用在镍-金属氢化物-电池中。此外一种这样的联合具有比纯聚烯烃无纺布更好的亲水性。这种联合的制备可比整理过了的聚烯烃制成的无纺布便宜得多。
本发明还涉及到包括下列步骤的制备上述无纺布的方法：
a)用已知的方法制备聚氧化烯均聚物或共聚物的纤维和
b)用已知的方法制成无纺布。
根据本发明的无纺布可在有化学腐蚀性物质的环境中使用。例如可作为电池的过滤材料或隔片，特别是用在具有碱性电解液的电池中。这种应用也是本发明的对象。
下述的实施例描述了本发明，但并不限制本发明。
用在DE-A4,301,373中描述的装置将商品聚合物“HostaformC52021”(Ticona GmbH)纺成纤维。聚合物首先在120℃下干燥8小时。纺丝的温度为215℃。根据聚合物的颗粒大小，纤维长度可在5mm至数厘米之间，这种纤维被加工制成干无纺布和湿无纺布。
纤维长度为40mm和纤度为3dtex的短纤维应用于加工制备干无纺布。用工艺装置由这种短纤维制备成具有单位面积重量为50g/m2宽为50cm的无纺布。通过点固化法固化。也可用聚丙烯-聚乙烯双组分-纤维的纤维份额为25％的纤维来制备无纺布，其在120-130℃下热固化。
用切短纤维(纤维长度为5mm)在薄板成形装置上制备湿无纺布。所得到的单位面积重量为50g/m2。
为了检测耐化学腐蚀性进行了下列实验：
1)在70℃下将纯POM无纺布放置在30％的氢氧化钾溶液中7天以上的时间。测得其质量损失小于0.5％。
2)在50℃下将纯POM无纺布放置在高锰酸钾溶液中24小时以上的时间。其质量损失大约为2％。
二个数值相应于传统隔片材料的数值。
为了检测无纺布的氨吸收能力，将无纺布放置在40℃的碱性的，0.3摩尔浓度的氨溶液中3天以上的时间。余氨用滴定分析法确定。大约5g的纤维或更确切地说无纺布的三个试样放置在添加5毫升0.3摩尔浓度氨溶液的120毫升8摩尔浓度的氢氧化钾溶液中3天以上的时间。同时放入没有被检测物质的三个空白试样。
放置后取出100毫升，用水蒸汽蒸馏法将氨转移入有150毫升蒸馏水的容器中，蒸馏水中含有10毫升0.1摩尔浓度的盐酸和几滴甲基红指示剂。酸用氢氧化钠反滴定。
这样所测得的氨吸收能力大约为每克0.5×10-4摩尔氨。

Claims (11)

1.一种含有聚氧化烯纤维的无纺布作为电池中的隔片的应用。
2.根据权利要求1的应用，其特征在于，聚氧化烯是一种聚合物，它具有化学式I的重复结构单元
-(CnH2n-O)-           (I)
式中n为1至4的整数。
3.根据权利要求1的应用，其特征在于，纤维具有0.1-30dtex的纤度。
4.根据权利要求1的应用，其特征在于，纤维是长丝。
5.根据权利要求1的应用，其特征在于，纤维是短纤维。
6.根据权利要求1的应用，其特征在于，具有5-500g/m2的单位面积重量。
7.根据权利要求1的应用，其特征在于，无纺布含有聚氧化烯纤维和聚酰胺纤维。
8.根据权利要求1的应用，其特征在于，无纺布含有聚氧化烯纤维和聚烯烃纤维。
9.根据权利要求1的应用，其特征在于，聚氧化烯纤维是用给予亲水性的或提高亲水性的化合物和/或步骤处理过的。
10.根据权利要求1的应用，其特征在于，所述电池为碱性电解液的电池。
11.根据权利要求2的应用，其特征在于，在式(I)中n为1或2。
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