CN1222057C - 具有锌电极的电池用的隔板 - Google Patents

具有锌电极的电池用的隔板 Download PDF

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CN1222057C
CN1222057C CNB011406283A CN01140628A CN1222057C CN 1222057 C CN1222057 C CN 1222057C CN B011406283 A CNB011406283 A CN B011406283A CN 01140628 A CN01140628 A CN 01140628A CN 1222057 C CN1222057 C CN 1222057C
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C·G·温斯雷
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Abstract

本发明涉及一种用于具有锌电极电池的隔板。该隔板的第一个实施方案包括微孔膜和在该膜至少一个表面上的涂层。该涂层包括醋酸纤维素和表面活性剂的混合物。该表面活性剂含有选自有机醚的活性组分。该隔板的第二个实施方案主要由微孔膜组成，其有效平均孔径小于0.045微米，厚度小于1.5密耳，电阻小于或等于30毫欧姆-英寸2，并且适于用电解质水溶液润湿。

Description

具有锌电极的电池用的隔板
技术领域
本发明涉及一种用于具有锌电极电池的隔板。
背景技术
具有锌电极的电池是众所周知的。参见US4359510；US4438185和US4544616；Tuck，C.D.S.，编辑，现代电池技术，Ellis HorwoodLimited，Chichester，England(1991)；和Linden，D.，编辑，电池手册，第二版，McGraw-Hill，Inc.，New York，NY(1995)，在这里将它们作为参考引入。此种电池中的一种为镍-锌(NiZn)电池。
虽然NiZn电池是公知的，但是它们在商业上从未获得重要的成功；显然，由于锌电极在可再充电电池体系中持续不久，因此限制了电池的有效循环寿命。已经建议可以将微孔膜与锌电极一起使用来解决该问题。参考Tuck，Ibid.，Linden，Ibid.，和US4359510；4438185以及4544616。
用于具有锌电极的电池中的一种市场有售的微孔膜是Celgard3406。参考：US4359510和4438185。Celgard 3406是在其一个表面上具有聚合物涂层的微孔膜。该微孔膜以Celgard2400微孔膜在市场上销售，它是一种平均孔径约为0.045微米的聚丙烯微孔膜。该聚合物涂层由醋酸纤维素和以商品名VICTAWET12润湿剂在市场有售的表面活性剂组成。VICTAWET12由Akzo Chemical，Inc.，Chicago，Illinois销售，且为一种具有2-乙基己基磷酸二氢酯的环氧乙烷聚合物。虽然Celgard3406能够充分发挥作用，但是它的存放期有限(从涂覆日起约9个月)并且它仅润湿一次(即，表面活性剂容易洗掉)。
因此，具有锌电极的电池需要改进的隔板，该隔板具有较高存放期，较高的再润湿能力，并且能够延长具有锌电极的可再充电电池的寿命。
发明内容
本发明涉及一种用于具有锌电极电池的隔板。该隔板的第一个实施方案包括微孔膜和在该膜至少一个表面上的涂层。该涂层包括醋酸纤维素和表面活性剂的混合物。该表面活性剂具有选自有机醚的活性组分。该隔膜的第二个实施方案主要由有效平均孔径小于0.045微米的微孔膜组成，其厚度小于1.5密耳(38.1微米)，电阻小于或等于20毫欧姆-英寸2(129毫欧姆-厘米2)，并且适于用含水电解质润湿。
具体实施方式
本发明涉及一种用于具有锌电极电池的隔板。那些电池典型的为二次电池(即，可再充电电池)。此种电池可以为镍-锌或银-锌电池。为了便于下述讨论，详细讨论的电池为镍-锌电池。但是本发明并不限于此。
镍-锌电池的化学组成是公知的。参考：Tuck，Ibid.，和Linden，Ibid.，两篇均引入本文以供参考。典型的，在此种体系中使用的电解质为氢氧化钾(KOH)水溶液，其中该氢氧化钾的浓度为约20-45重量％。典型的电池包括镍电极、锌电极、电解质和隔板，例如微孔膜。通常，电极夹着隔板，并且电解质通过隔板与两个电极相通。
根据本发明的隔板具有两个实施方案。通常，第一个实施方案涉及一种涂覆的隔板，而第二个实施方案是一种未涂覆的隔板。每个实施方案将在下面依次讨论。优选的，下述隔板中的每个在31％KOH水溶液中具有小于或等于30毫欧姆-英寸2(193.5毫欧姆-厘米2)的电阻，更优选，该隔板在31％KOH水溶液中的电阻≤20毫欧姆-英寸2(129毫欧姆-厘米2)，并且最优选，在31％KOH水溶液中，电阻在约10-12毫欧姆-英寸2(64.5-77.4毫欧姆-厘米2)范围内。该电阻(或电阻率)按照下述方法测量：使用R.A.I.AC Milliohm Resistance Meter，型号2401和R.A.I.测试电池电极(由RAIResearch Corp.，Hauppauge，NY提供)。用31重量％的KOH润湿试样(测试前，试样应在溶液中浸渍8-24小时)。试样在测试时不应干燥。对材料的三个试样进行测试并取平均值。而后，以毫欧姆-英寸2计的结果可以除以材料的厚度，并以欧姆-英寸/密耳计。
第一个实施方案是涂覆的隔板。该隔板包括微孔膜和在该膜至少一个表面上的涂层。表面活性剂具有选自有机醚的活性组分。上述每种组分将在下文中更为详细地论述。
该微孔膜通常为疏水的聚烯烃聚合物。该疏水的聚烯烃聚合物包括，例如，聚乙烯、聚丙烯，后者是优选的。该膜的制备方法没有严格限制，并且可包括，例如，“干”拉伸(或Celgard)法，或者“溶剂”拉伸(或逆相)法。此种膜的厚度可以为小于3密耳(约75微米)，优选为小于1.5密耳(38微米)，并且最优选为厚度为约1密耳(25微米)。该膜的平均孔径可以为约0.045±0.002微米，孔隙率为28-40％，并且Gurley为20-45秒/英寸2(3.1-7.0秒/厘米2)。此种膜可由诸如Celgard Inc.，Charlotte，North Carolina，U.S.A.；Tonen K.K.，Tokyo，Japan；AsahiChemical Co.，Tokyo，Japan；Ube Industries，Tokyo，Japan；和NittoDenko Corporation，Tokyo，Japan商购到。
该涂层涂覆在该膜的至少一个表面上。如果涂覆在一个表面上，该涂层表面密度可在约0.12-0.80毫克/cm2范围内，并且优选为，该表面密度可在0.25-0.45毫克/cm2范围内。该涂层优选以溶液形式涂覆，并且该溶剂(例如，丙酮或甲基乙基酮)以任何公知方法驱除。涂覆的隔板的有效平均孔径应为小于0.045微米，成选为0.030-0.040微米，并且最优选为小于0.035微米。有效平均孔径太大将对循环寿命产生负面影响，因为太多锌离子将穿过该隔板，而如果有效平均孔径太小，将对电池内部的电导率产生负面影响，因为电阻将太高。该有效平均孔径指的是当用电解质润湿时，涂覆的隔板表现出来的表面孔隙直径。有效平均孔径用溶质通过方法测量。参考诸如：Cheryan，M.， Ultrafiltration Handbook(超滤手册)，Technomic Publishing Co.，Lancaster，PA，(1986)p.62-71。通过上述方法，使用：肌肉球蛋白-17600分子量(MW)，尺寸为3.7纳米(nm)，0％拒绝；乳球蛋白-38000MW，5.2nm，10％；白蛋白-69000MW，6.4nm，30％；血清球蛋白-148000MW，9.2nm，75％；血蓝蛋白(Palinurus)-450000MW，11.7nm，90％，该膜的孔径被评估为0.035微米(35nm)。
该涂层包括醋酸纤维素和表面活性剂的混合物。该醋酸纤维素(每个葡萄糖上含有约2.5个乙酰基团，例如，CA-398-3)是可商购的原料，例如，Celanese Acetate LLC，Charlotte，North Carolina，U.S.A.；或者Eastman Chemical Co.，Kingsport，Tennwesee，U.S.A..其中Celanese醋酸纤维素HB-105是优选的。
关于表面活性剂，三个因素有助于限定选择的标准，那些因素是：1)该表面活性剂必须是对电解质惰性的(例如，在电解质中是不可水解的)；2)该表面活性剂在电解质中应为不可溶的或为不易溶的；并且3)该表面活性剂应粘附在膜上(即，不容易从膜上洗掉)。满足上述标准的一种表面活性剂具有选自有机醚的活性组分。该有机醚的一个实例为壬基苯氧基聚(乙烯氧基)乙醇。一种该表面活性剂可由Rhone-Poulenc(Cranbury，New Jersey，U.S.A.)以商品名IGEPAL CO-530商购到。
在选择涂层的醋酸纤维素和表面活性剂组分的含量时，考虑下述因素：对于醋酸纤维素，采用润湿时足以涂覆表面以产生筛孔效应(即，基于尺寸，可选择性通过/拒绝分子的能力)的量，但是太多将阻塞孔隙并增加电阻；对于表面活性剂，采用足以润湿电解质的量，但是太多将阻塞孔隙。涂层的醋酸纤维素可在约0.02mg/cm2-0.30mg/cm2范围内，优选为0.05-0.15mg/cm2，并且表面活性剂(即，IGEPAL)可在约0.10-0.50mg/cm2范围内，优选为0.20-0.30mg/cm2。
第二个实施方案为未涂覆的隔板(即，无醋酸纤维素涂层)。该隔板主要由有效平均孔径小于0.045微米且适于用电解质水溶液润湿的微孔膜组成。上述每种组分将在下文中详细论述。
该微孔膜通常为疏水的聚烯烃聚合物。此种聚合物包括，例如，聚乙烯和聚丙烯，后者是优选的。该膜的制备方法没有严格限制，并且可包括，例如，“干”拉伸(或Celgard)法，或者“溶剂”拉伸(或逆相)法。此种膜的厚度可以为约1.5密耳(38微米)或更小。此种膜没有涂层，因为其有效平均孔径可以阻止在激活的电池中电解质流中的锌离子穿过该隔板。该有效平均孔径应小于0.045微米，优选为小于0.035微米，并且最优选在0.020-0.040微米范围内。太大的有效平均孔径将对循环寿命产生负面影响，因为太多的锌离子将穿过隔板，而如果有效平均孔径太小，将对电池内部的电导率产生负面影响，因为电阻将太高。该实施方案中的润湿涉及用表面活性剂(例如，润湿剂)使表面改性。该表面活性剂具有选自有机醚的活性组分。该有机醚的一个实例为壬基苯氧基聚(乙烯氧基)乙醇。一种该表面活性剂可由Rhone-Poulenc(Cranbury，New Jersey，U.S.A.)以商品名IGEPAL CO-530商购到。在选择表面活性剂的含量时，考虑下述因素：足以润湿电解质的量，但是太高将阻塞孔隙。该表面活性剂(即，IGEPAL)可以在约0.10-0.50mg/cm2范围内，优选为0.20-0.30mg/cm2。
                            实施例
根据本发明制备的隔板与可商购的制品Celgard3406微孔膜进行比较。本发明特别的涂层溶液包括，以溶剂重量为基，3.5％的醋酸纤维素和8％的IGEPAL CO-530，并且甲基乙基酮是溶剂。比较的结果如下：
                          表
                   3406              本发明
表面活性剂耐久性  涂覆日起9个月     涂覆日起18个月
润湿性能          润湿一次，干燥    反复润湿＞5次
                  后不能再润湿
本发明可以用其他的特定形式具体表达，而不偏离其精神或主旨，因此应参考所附的权利要求书，而不是上述说明书，作为本发明范围的指示。

Claims (7)

1、一种电池隔板，包括
微孔膜和
在所述膜的至少一个表面上的涂层，所述涂层包括醋酸纤维素和表面活性剂，所述表面活性剂含有选自有机醚的活性组分。
2、根据权利要求1的隔板，具有小于0.045微米的有效平均孔径。
3、根据权利要求1的隔板，其中所述醋酸纤维素在每个葡萄糖上含有约2.5个乙酰基团。
4、根据权利要求1的隔板，其中所述涂层的表面密度为0.12-0.80mg/cm2。
5、根据权利要求1的隔板，具有小于或等于193.5毫欧姆-厘米2的电阻。
6、根据权利要求5的隔板，其中所述电阻在64.5-77.4毫欧姆-厘米2范围内。
7、一种具有锌电极的电池，包括
第一电极；
第二电极；
电解质；和
根据权利要求1的隔板，所述隔板设置于所述第一电极和所述第二电极之间，并且所述电解质通过所述隔板与所述电极相通。
CNB011406283A 2000-09-21 2001-09-19 具有锌电极的电池用的隔板 Expired - Fee Related CN1222057C (zh)

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