CN104969381A - 用于电化学电池的分隔体介质 - Google Patents

用于电化学电池的分隔体介质 Download PDF

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CN104969381A
CN104969381A CN201380059560.8A CN201380059560A CN104969381A CN 104969381 A CN104969381 A CN 104969381A CN 201380059560 A CN201380059560 A CN 201380059560A CN 104969381 A CN104969381 A CN 104969381A
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nonwoven sheet
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CN104969381B (zh
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H.S.林
P.阿罗拉
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DuPont Safety and Construction Inc
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Abstract

本发明公开了用于电化学电池的分隔体介质，其包含至少一种聚合物纤维的非织造片材。所述非织造片材具有约0.5至约1.5m2/g的表面积并具有等于或大于2.5倍中流量孔尺寸且大于11倍最小孔尺寸的最大孔尺寸。所述片材可被磺化至0.67％的含量并且在磺化后相对于之前已知的分隔体展示优异的拉伸特性。

Description

用于电化学电池的分隔体介质
背景技术
1.技术领域
本发明涉及用于电化学电池、尤其是碱性电池的分隔体领域。
2.相关领域的描述
因为它们的高能量密度，碱性电池已经变得越来越流行。同样地，这些电池越来越多地用于通常为传统铅酸电池系统保留的应用中。
为了在碱性系统中获得延长的电池寿命和效率，需要使用电池分隔体。将电池分隔体定位在阳极板和阴极板之间以便提供，(1)相反电荷的电极之间的分隔，(2)电解质储槽，(3)横跨电极表面的均匀电解质分布以便允许均匀的电流密度，以及(4)电极膨胀的空间。
目前在碱性电池中使用的电池分隔体通常由聚烯烃，优选地聚丙烯、聚酰胺或尼龙非织造材料片材形成。
镍金属氢化物(NiMH)电池系统中的主要缺陷之一是它们的高自放电速率，即，在储存期间持续损失它们的电量。“氨-穿梭”对自放电具有主要影响。氧化Ni电极中的含氮杂质以形成硝酸根，其通过分隔体迁移到阴极中。在阴极处将硝酸根还原成氨。氨再次通过分隔体并到达镍电极，并且完成穿梭。
发明内容
本发明涉及用于电化学电池的分隔体介质，其中电化学电池可为蓄电池或电容器。在一个实施例中，介质包括至少一个非织造片材，其包含聚合物纤维，其中该非织造片材具有约0.5至约1.5m2/g的表面积，并且其中非织造片材具有等于或大于2.5倍中流量孔尺寸且大于11倍最小孔尺寸的最大孔尺寸。
本发明涉及用于碱性电池的分隔体介质，并且具体地涉及镍金属氢化物电池。在一个实施例中，介质包括至少一个非织造片材，其包含聚合物纤维，其中该非织造片材具有约0.5至约1.5m2/g的表面积，并且其中该非织造片材具有等于或大于2.5倍中流量孔尺寸且大于11倍最小孔尺寸的最大孔尺寸。在另一个实施例中，聚合物纤维是磺化的并含有至少0.67重量％的硫。在另一个实施例中，相对于未经受磺化的介质，分隔体保留了其纵向(MD)拉伸强度的至少70％。
本发明还涉及制备用于电化学电池的分隔体介质的方法。
本发明还涉及电化学电池，其中该电池是包括分隔体介质的碱性电池，该分隔体介质进一步包括至少一个非织造片材，其包含聚合物纤维，其中该非织造片材具有约0.5至约1.5m2/g的表面积，并且其中该非织造片材具有等于或大于2.5倍中流量孔尺寸且大于11倍最小孔尺寸的最大孔尺寸，该聚合物纤维是磺化的并含有至少0.67重量％的硫，并且其中相对于未经受磺化的介质，该分隔体保留了其纵向(MD)拉伸强度的至少70％。
具体实施方式
申请人特别将所有引用的参考文献的完整内容引入本公开内容中。此外，当量、浓度或其他值或参数以范围、优选范围或优选上限数值和优选下限数值的列表形式给出时，其应理解为具体地公开由任何范围上限或优选数值和任何范围下限或优选数值的任何一对所构成的所有范围，而无论所述范围是否被单独地公开。凡在本文中给出某一数值范围之处，该范围都旨在包括其端点，以及位于该范围内的所有整数和分数，除非另行指出。不旨在将本发明的范围限制为限定范围时详述的具体值。
定义
如本文所用，术语“聚合物”通常包括但不限于均聚物、共聚物(诸如例如，嵌段、接枝、无规和间规共聚物)、三元共聚物等，以及它们的共混物和改性形式。此外，除非另外具体限定，术语“聚合物”应包括所述材料所有可能的几何构型。这些构型包括但不限于全同立构、间同立构、以及无规对称。
如本文所用，术语“聚烯烃”旨在表示仅由碳和氢组成的基本饱和的聚合物烃类系列中的任一种。典型的聚烯烃包括但不限于聚乙烯、聚丙烯、聚甲基戊烯、以及单体乙烯、丙烯和甲基戊烯的各种组合。
如本文所用，术语“聚乙烯”旨在不仅涵盖乙烯的均聚物，而且涵盖其中至少85％的重复单元为乙烯单元的共聚物诸如乙烯和α-烯烃的共聚物。优选的聚乙烯包括低密度聚乙烯、线性低密度聚乙烯、和线性高密度聚乙烯。优选的线性高密度聚乙烯具有约130℃至140℃的熔点范围上限，约0.941至0.980克每立方厘米范围内的密度，以及0.1至100之间、并优选小于4的熔融指数(由ASTM D-1238-57T条件E定义)。
如本文所用，术语“聚丙烯”旨在不仅涵盖丙烯的均聚物，而且涵盖其中至少85％的重复单元为丙烯单元的共聚物。优选的聚丙烯聚合物包括全同立构聚丙烯以及间同立构聚丙烯。
如本文所用，术语“非织造片材”表示以无规方式定位以形成平面材料而没有如针织物中可辨别的图案的各个纤维或线的结构。
如本文所用，术语“丛丝”表示多个无规长度的薄、带状、薄膜-原纤元件的三维整体网络或纤维网。通常，它们具有小于约4微米的平均膜厚度和小于约25微米的中值原纤宽度。如果数学转换成圆面积，则平均膜-原纤截面积将产生约1微米至25微米之间的有效直径。在丛丝结构中，薄膜-原纤元件以不规则间隔在贯穿该结构的长度、宽度和厚度的多个位置间歇联合并分离以形成连续的三维网络。
“磺化”是指含硫部分化学结合纤维所包含的聚合物的至少一部分。磺化可通过本领域技术人员已知的任何方法进行。例如，磺化可使用US3,684,554中所述的纤维网气相表面磺化进行。基本方法涉及使干燥聚合物纤维网与连续的一股气态SO3流(在干燥惰性气体中2-15％的体积)接触，其能够连续高速(100-200英尺/秒)运行。磺化的聚合物纤维网可用去离子水冲洗。磺化也可通过美国专利6,403,265的方法，使用浓硫酸进行。
描述
本发明克服了当前使用的分隔体固有的问题并且提供一种可润湿的片材材料，其具有期望的拉伸强度、氨吸收特性、电解质吸收和电阻性能，这是可用于碱性电池的。
因此本发明的目的是为了提供一种可润湿的片材材料，其在碱性电池中用作分隔体。本发明的另一目的是为了提供一种片材材料，它是可通过电解质润湿的并且在碱性电池系统中具有良好的电解质吸收和氨吸收。
因此本发明涉及用于碱性电池的分隔体介质，并且具体地涉及镍金属氢化物电池。在一个实施例中，介质包括至少一个非织造片材，其包含聚合物纤维，其中该非织造片材具有约0.5至约1.5m2/g的表面积，并且其中该非织造片材具有等于或大于2.5倍中流量孔尺寸且大于11倍最小孔尺寸的最大孔尺寸。在另一个实施例中，聚合物纤维是磺化的并含有至少0.67重量％的硫。在另一个实施例中，相对于未经受磺化的介质，分隔体保留了其纵向(MD)拉伸强度的至少70％。
聚合物纤维可包含选自聚烯烃、聚酯、聚酰胺、芳族聚酰胺、聚砜、聚酰亚胺、氟化聚合物以及它们的各种组合的聚合物。当聚合物纤维由聚烯烃制成时，聚合物可选自聚乙烯、聚丙烯、聚丁烯和聚甲基戊烯。
用于碱性电池分隔体的合适聚合物还包括脂族聚酰胺、半芳族聚酰胺、聚乙烯醇、纤维素、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丙二醇酯、聚对苯二酸丁二醇酯、聚砜、聚偏氟乙烯、聚甲基戊烯、聚苯硫醚、聚缩醛、聚丙烯腈、聚氨酯、芳族聚酰胺、以及它们的各种共混物、混合物和共聚物。尤其适用于碱性电池分隔体的聚合物包含聚乙烯醇、纤维素、脂族聚酰胺和聚砜。
聚合物纤维可为丛丝纤维束。此外聚合物纤维可具有非圆形截面。
在另一个实施例中，非织造片材为单向经拉伸的非织造片材，其中拉伸已经沿纵向发生。此外非织造片材可具有约0.5至约1.0m2/g的表面积。
在另一个实施例中，非织造片材由纤维组成，100％的该纤维具有大于1微米的数均纤维直径。
非织造片材可具有0.20毫摩尔/克的氨捕集和至少16牛顿/厘米(N/cm)的纵向拉伸强度保持。
本发明还涉及制备用于电化学电池的分隔体介质的方法。该方法包括以下步骤：
(i)在约205℃至220℃的纺丝温度下将12重量％至24重量％聚乙烯在纺丝剂中的溶液闪蒸纺丝以形成丛丝纤维束，，并将所述丛丝纤维束收集成未粘结纤维网，其中所述纺丝剂由正戊烷与环戊烷的混合物组成；
(ii)在温度处于约124℃至约154℃之间且定位成分开约5cm至约30cm之间的加热拉伸辊之间，将所述未粘结纤维网沿纵向单向拉伸，并拉伸约3％至25％之间以形成经拉伸的纤维网；以及
(iii)在温度处于约124℃至约154℃之间的加热粘结辊之间粘结经拉伸的纤维网以形成非织造片材，其中该非织造片材具有约0.5至约1.5m2/g的表面积，以及
大于2.5倍中流量孔尺寸和大于11倍最小孔尺寸的最大孔尺寸。
制备分隔体介质的方法还可包括在粘结经拉伸的纤维网后使非织造片材磺化。
本发明还涉及电化学电池，其中该电池是包括分隔体介质的碱性电池，该分隔体介质进一步包括至少一个非织造片材，其包含聚合物纤维，其中该非织造片材具有约0.5至约1.5m2/g的表面积，并且其中该非织造片材具有等于或大于2.5倍中流量孔尺寸且大于11倍最小孔尺寸的最大孔尺寸，该聚合物纤维是磺化的并含有至少0.67重量％的硫，并且其中相对于未经受磺化的介质，该分隔体保留了其纵向(MD)拉伸强度的至少70％。
所述电池可为碱性一次电池，例如其中阳极为锌且阴极为锰氧化物(MnO2)的锌-锰氧化物或Zn-MnO2电池，或其中阳极为锌且阴极为空气的锌-空气电池，或者其可为碱性二次电池，例如其中阳极为镉且阴极为羟基氧化镍(NiOOH)的镍镉电池、其中阳极为锌且阴极为NiOOH的镍-锌或Ni-Zn电池、其中阳极为金属氢化物(例如LaNi5)且阴极为NiOOH的镍金属氢化物(NiMH)电池或其中阳极为氢(H2)且阴极为NiOOH的镍-氢或NiH2电池。其它类型的碱性电池包括其中阳极为锌且阴极为氧化汞(HgO)的锌/氧化汞，其中阳极为镉且阴极为氧化汞的镉/氧化汞，其中阳极为锌且阴极为氧化银(AgO)的锌/氧化银，其中阳极为镉且阴极为氧化银的镉/氧化银。所有这些电池类型均利用30％至40％的氢氧化钾作为电解质。
本发明的这个实施例的碱性电池可包括分隔体，其具有小于约300milliohms-cm2，优选地小于200milliohms-cm2，最优选地小于100mohms-cm2的离子电阻，该离子电阻在1KHz下，在35％的氢氧化钾电解质溶液中进行测量。
在本发明的一些实施例中，可优选交联聚合细纤维以维持多孔结构并改善电解质中分隔体的结构完整性。
在本发明的一些实施例中，可优选在形成电池之前用表面活性剂涂覆分隔体以改善在30-40％KOH电解质中的可润湿性和芯吸性能。表面活性剂是在强碱性环境下稳定的，例如离子表面活性剂。另选地，分隔体能够发生丙烯酸接枝以改善分隔体的可润湿性。
实例
测试方法
KOH电解质中的离子电阻为分隔体抗离子流动的量度，并且如下测定。将样本切成小块(1″×1″)并浸泡在35％的氢氧化钾中过夜，以确保完全润湿。将样本置于两个隔片之间，并且有暴露样本的1cm2的窗口。将隔片和样本的夹心层置于电阻电池之间，该电池具有两个铂电极，使得窗口面朝两个电极。电阻在1KHz下使用HP毫欧计进行测量。在隔片之间无任何分隔体的情况下重复该测量。两个读数之间的差值是样本的电阻(毫欧)。分隔体电阻随后乘以电极面积(在这种情况下1cm2)并且以milliohms-cm2记录结果。
基重通过ASTM D-3776来测量，其以引用方式并入并以g/m2为单位进行记录。
孔隙率通过用样本基重(单位为g/m2)除以聚合物密度(单位为g/cm3)并除以样本厚度(单位为微米)，乘以100并随后从100％中减去来计算，即孔隙率百分比＝100-基重/(密度×厚度)×100。
纤维直径按如下方法测定。在5,000倍放大倍数下对每个细纤维层样本拍摄十个扫描电镜(SEM)图像。由照片测量十一(11)个清晰可辨的细纤维的直径并进行记录。不包括缺陷(即，细旦纤维的团块、聚合物小滴、细旦纤维的交叉点)。计算每个样本的平均(中值)纤维直径。
厚度通过ASTM D1777测量，其据此以引用方式并入，记录为密耳并转化成微米。
平均流孔径根据ASTM命名E 1294-89，“Standard Test Method forPore Size Characteristics of Membrane Filters Using Automated LiquidPorosimeter”进行测量，其通过利用ASTM命名F316中的自动泡点法使用毛细流动孔隙率计(型号CFP-34RTF8A-3-6-L4，Porous Materials，Inc.(PMI)，Ithaca，NY)大致测量具有0.05μm至300μm的孔径直径的膜的孔径特性。各个样本(8、20或30mm直径)用低表面张力流体(1，1，2，3，3，3-六氟丙烯，或“Galwick”，具有16达因/厘米的表面张力)润湿。将每个样本置于夹持器中，然后施加空气压差并将流体从样本上移除。润湿流量等于干燥流量(无润湿溶剂下的流量)的二分之一处的压差用于利用提供的软件来计算中流量孔径。
拉伸强度根据ASTM D5035-95，“Standard Test Method for BreakingForce and Elongation of Textile Fabrics(Strip Method)”进行测量，并且以kg/cm2为单位进行记录。
表面积使用BET方法进行测量。Branaur，Emmet and Teller(BET)理论将固体表面上的气体吸收量与表面积关联。将一克样本置于样本室中并置于液氮中以在真空下脱气。在已经从样本表面去除任何表面吸收的气体之后，将氮气引入样本中。测量表面吸收消耗的氮气体积并将其与表面积关联。
氨捕集能力通过ASTM D7129-09“Standard test method fordetermination of ammonia trapping in a grafted battery separator”进行测量。该测试测量当预定量的分隔体和氢氧化铵在受控温度下处理一天时，由分隔体保持的氨量。
如公布于1972年8月15日的US 3,684,554中所述，使用纤维网的气相表面磺化对拉伸粘结的非织造纤维网进行四种不同水平的磺化。基本方法涉及使干燥聚合物纤维网与连续的一股气态SO3流(在干燥惰性气体中2-15％的体积)接触，其能够连续高速(100-200英尺/秒)运行。磺化的聚合物纤维网用去离子水冲洗。
在磺化样本上的％硫含量通过Micro-Analysis，Inc.，(WilmingtonDE.)进行测量硫分析通过两种方法之一进行。在Carlo Erba 1108硫自动分析仪中，将样本在电子微量天平上称重并随后引入自动分析仪中，该仪器保持在正压下，带有氦气载气。动态闪速燃烧在氧气环境中发生在大约1400℃下。定量燃烧通过使气体混合物通过在氧化铝上的钨酸酐以去除任何氟，并且随后在氧化剂钨酸酐上完成。混合物随后通过铜以去除过量的氧，并且用于将氮氧化物还原成元素氮。将所得混合物导向色谱柱，其包含Perapak PQS，将其保持在60℃-80℃范围内的恒定温度下，并且分离各个组分并将硫洗脱成二氧化硫。用热导率检测器测量二氧化硫，将它的信号导入计算机用于数据处理。
使用LECO CHNS·932分析仪，在CHNS分析中的燃烧产物是CO2、H2O、NOx、和SOx。通过氦气载体携载通过系统的气体被吹扫通过氧化管，其装有WO3和铜。铜去除过量的氧以完成向SO2的转化。将氮氧化物还原成N2。将气体混合物吹扫通过H2O红外检测电池，并且随后通过水捕集器，其中H2O被去除。随后剩余的气体混合物分别通过SO2、和CO2lR电池。随后去除SO2、和CO2，并且使N2通过热导率检测器。将信号导入计算机用于数据处理。
代表本发明非织造片材的实例1和2由美国专利7,744,989(其以引用的方式并入本文)中所公开的闪蒸纺丝技术和片材粘结前附加的热拉伸制成。未粘结的非织造片材由熔融指数为0.7g/10min(根据ASTM D-1238在190℃和2.16kg载荷下测量)的20重量％浓度的高密度聚乙烯的纺丝剂(60重量％正戊烷和40重量％环戊烷)溶液闪蒸纺丝。实例1和2的未粘结非织造片材被拉伸并粘结整个表面。使所述片材在146℃下的预热辊、两对146℃下的粘结辊(片材的每面各一个辊)、由满足85-90肖氏硬度A的配制橡胶制成的146℃下的支承辊、以及两个冷却辊之间运行。实例1和2在146℃的粘结温度下，以30.5m/min的速率在两个预热辊之间拉伸20％，它们具有10cm的跨越长度。实例1在500PLI的辊隙压力下进行压延，并且实例2不进行压延。比较例A是1056D(购自DuPont ofWilmington，DE)，它是一种市售闪纺非织造片材产品，基重为54.4gsm。片材的物理特性在表1和2中给出。
除了无需片材拉伸之外，与实例1和2相似地制备比较例B。如美国专利7,744,989中所公开的将未粘结的非织造片材整个表面粘结。在359kPa蒸汽压和91m/min的速度下，使片材的每个面在平滑的蒸汽辊上运行。
比较例C和D是市售的纺粘-熔喷-纺粘法(SMS)层合产品，购自Midwest Filtration Co.Cincinnati，OH，并且比较例E是市售的非织造材料，由聚丙烯制成，并且用作NiMH电池的分隔体。
表1和2示出本发明的实例如何与测试的比较例进行比较。表1和2中的数据用于未被磺化的样本。
表1：
样本 基重(克/米 2 ) 厚度(μm)10KPa 孔隙率(％)(计算的)
实例1 37.3 91.4 57.5％
实例2 40.7 182.9 76.8％
比较例A 54.2 172.7 67.2％
比较例B 54.6 234.3 75.7％
比较例C 61.0 381.2 83.3％
比较例D 88.1 491.7 81.3％
比较例E 63.8 144.2 53.8％
表2：
表3示出在磺化之前和之后获得的结果。实例1-1和2-1展示在磺化后优异的氨捕集能力，并且仅少量损失了拉伸强度。
表3：

Claims (15)

1.一种用于电化学电池的分隔体介质，所述分隔体介质包括至少一个非织造片材，所述非织造片材包含聚合物纤维，其中所述非织造片材具有0.5至1.5m2/g的表面积，并且相对于未经受磺化的介质，所述分隔体保留了其纵向(MD)拉伸强度的至少70％。
2.根据权利要求1所述的分隔体介质，其中所述聚合物纤维是磺化的并含有至少0.67重量％的硫。
3.根据权利要求1所述的分隔体介质，其中所述聚合物纤维包含选自以下的聚合物：聚烯烃、聚酯、聚酰胺、芳族聚酰胺、聚砜、聚酰亚胺、氟化聚合物以及它们的各种组合。
4.根据权利要求3所述的分隔体介质，其中所述聚合物纤维由聚烯烃聚合物制成，所述聚烯烃聚合物选自聚乙烯、聚丙烯、聚丁烯和聚甲基戊烯。
5.根据权利要求1所述的分隔体介质，其中所述聚合物纤维具有非圆形截面。
6.根据权利要求1所述的分隔体介质，其中所述聚合物纤维为丛丝纤维束。
7.根据权利要求1所述的分隔体介质，其中所述非织造片材为沿纵向单向拉伸的非织造片材。
8.根据权利要求1所述的分隔体介质，其中所述非织造片材具有0.5至1.0m2/g的表面积。
9.根据权利要求1所述的分隔体介质，其中所述非织造片材由纤维组成，100％的所述纤维具有大于1微米的数均纤维直径。
10.根据权利要求1所述的分隔体介质，其中所述非织造片材具有0.20毫摩尔/克的氨捕集能力和至少16牛顿/厘米(N/cm)的纵向拉伸强度保持。
11.根据权利要求1所述的分隔体介质，其中所述非织造片材具有等于或大于2.5倍中流量孔尺寸且大于11倍最小孔尺寸的最大孔尺寸。
12.一种制备用于电化学电池的分隔体介质的方法，所述方法包括：
在205℃至220℃的纺丝温度下将12重量％至24重量％聚乙烯在纺丝剂中的溶液闪蒸纺丝以形成丛丝纤维束，并将所述丛丝纤维束收集成未粘结纤维网，其中所述纺丝剂由正戊烷与环戊烷的混合物组成；
在温度处于124℃至154℃之间且定位成分开5cm至30cm之间的加热拉伸辊之间，将所述未粘结纤维网沿纵向单向拉伸，并拉伸3％至25％之间以形成经拉伸的纤维网；以及
在温度处于124℃至154℃之间的加热粘结辊之间粘结所述经拉伸的纤维网以形成非织造片材，其中所述非织造片材具有0.5至约1.5m2/g的表面积，以及
大于2.5倍中流量孔尺寸且大于11倍最小孔尺寸的最大孔尺寸。
13.根据权利要求12所述的用于制备分隔体介质的方法，所述方法还包括在粘结所述经拉伸的纤维网后使所述非织造片材磺化。
14.根据权利要求1所述的电化学电池，其中所述电池是蓄电池或电容器。
15.一种电化学电池，其中所述电池是包括分隔体介质的碱性电池，所述分隔体介质进一步包括至少一个非织造片材，其包含聚合物纤维，其中所述非织造片材具有0.5至1.5m2/g的表面积，并且其中所述非织造片材具有等于或大于2.5倍中流量孔尺寸且大于11倍最小孔尺寸的最大孔尺寸，所述聚合物纤维是磺化的并含有至少0.67重量％的硫，并且其中相对于未经受磺化的介质，所述分隔体保留了其纵向(MD)拉伸强度的至少70％。
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