CN101268580A - 作为用于电池及燃料电池应用的隔离件的聚电解质膜 - Google Patents

作为用于电池及燃料电池应用的隔离件的聚电解质膜 Download PDF

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CN101268580A
CN101268580A CNA2006800344794A CN200680034479A CN101268580A CN 101268580 A CN101268580 A CN 101268580A CN A2006800344794 A CNA2006800344794 A CN A2006800344794A CN 200680034479 A CN200680034479 A CN 200680034479A CN 101268580 A CN101268580 A CN 101268580A
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李琳风
马富源
B·F·库科维特斯基
S·M·法里斯
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Abstract

本发明提供了能够阻止可充电电池中枝晶生长，具有低内生电阻的聚电解质膜作为隔离件，其具有高离子传导性，并阻止直接燃料供给燃料电池中的燃料穿透。本发明还提供了用于形成所述聚电解质膜的节省成本的方法。本发明描述的聚电解质膜可用于电化学电池(例如，一次电池、二次电池，如Ag－Zn、Ni－Zn、Ni－MH、Li聚合物及Li－离子二次电池；燃料电池，包括但不限于金属空气电池或燃料电池、质子交换膜氢燃料电池、直接液体供给燃料电池)中。

Description

作为用于电池及燃料电池应用的隔离件的聚电解质膜
发明领域
本发明涉及用于电池及燃料电池的隔离件，特别是具有高离子传导性的电绝缘隔离件。
背景技术
枝晶生长是可充电电池失效的常见原因。枝晶生长是电池充电期间发生的现象，由此，活性材料(通常为例如锌或锂的金属)被从氧化态还原，并沉积于基材(例如，正在充电的电极)上。依据充电条件，所述金属可呈树枝形式沉积，并可能穿透隔离件或膜，并使电池短路。
传统的膜或隔离件无法有效阻止可充电电池或燃料电池中的枝晶生长。例如，在Ni-Zn电池、Ag-Zn电池、Zn-空气电池及燃料电池中，锌枝晶生长是常见的问题。在可充电的锂电池中，锂枝晶生长也很常见。
很多市售隔离件或膜以减小孔洞大小来避免枝晶。然而，孔洞大小的减小通常会造成电阻增大和离子传导性降低。更重要的是，仅通过减小孔洞大小不可能有效阻止枝晶。
在一些市售隔离件或膜中，使用化学反应来阻止枝晶。然而，这要求化学试剂的再生，否则会消耗反应物。
对于可充电电池而言，具有高循环次数(即，循环寿命)是重要的。电池组件(比如，膜)易于制造与节省成本也很重要。所述膜还需具有高离子传导性与低电阻。本领域中仍然需要具有这些特性的膜。
另外，常常用于直接液体供给(例如，甲醇、NaBH4、LiBH4)的燃料电池应用中。然而，燃料穿透(fuel crossover)也是常见的问题。非常需要能够阻止燃料穿透的膜。
发明概述
本发明提供了能够阻止可充电电池中枝晶生长，具有低内生电阻的聚电解质膜作为隔离件，其具有高离子传导性，并阻止直接燃料供给燃料电池中的燃料穿透。本发明还提供了用于形成所述聚电解质膜的节省成本的方法。
本发明描述的聚电解质膜可用于电化学电池(例如，一次电池、二次电池，如Ag-Zn、Ni-Zn、Ni-MH、Li聚合物及Li-离子二次电池；燃料电池，包括但不限于金属空气电池或燃料电池、质子交换膜氢燃料电池、直接液体供给燃料电池)中。
附图说明
结合附图阅读时，可以更好地理解前述发明概述及后面的本发明优选实施方案的详细描述。为了说明本发明的目的，附图中显示了本发明优选的实施方案。但是，应当理解，本发明不严格限于所示的布置与方式。附
图中：
图1是根据本发明所形成的膜的示意图；以及
图2是本发明的一些实施例中使用的测试设备的示意图。
发明详述
本发明提供的聚电解质膜包括带电聚合物链。特别的，带相反电荷的聚电解质层叠，并且在聚合物链的交界处形成双电层(electrical doublelayer)(参见图1)。由此，所述聚合物以静电方式结合在一起。
在一些实施方案中，聚电解质膜可通过将基材依序浸入带负电聚电解质(即，聚阴离子)溶液中，而后浸入带正电聚电解质(即，聚阳离子)溶液中(反之亦可)而一层层地制备。在进一步的实施方案中，以循环方式重复该过程，以制备聚电解质多层膜。
新型特性(包括电学、磁学及光学特性)可以使用带相反电荷的聚合物，通过这里所述的简单、低成本及湿式蚀刻清洗系统(wet-bench)技术得到。
带正电的聚合物(聚阳离子)的实例包括但不限于聚(二烯丙基二甲基氯化铵)、聚(N-甲基-4-乙烯基吡啶碘化物)、聚(烯丙胺盐酸盐)、聚(丙烯酸丁酯-共-N-甲基-4-乙烯基吡啶碘化物)、聚(丁二烯-共-N-甲基-4-乙烯基吡啶)碘化物、聚(苯乙烯-共-4-乙烯基吡啶)、聚(丙烯酸乙酯-共-4-乙烯基吡啶)、聚苯胺基聚合物、聚吡咯基聚合物及其它合适的聚阳离子。
在一个实施方案中，聚阳离子可具有下列一般结构：
Figure A20068003447900071
其中R1是-CH3、-CH2CH3、-CH2CH2CH3、-(CH2)nCH3；R2是-CH3、-CH2CH3、-CH2CH2CH3、-(CH2)nCH3；X是Cl-、Bl-、I-、F-、CO3 2-、SO4 2-、PO4 3-等。
具有上述式1的聚合物的实例包括但不限于，聚(二烯丙基二甲基氯化铵)、聚(烯丙胺盐酸盐)。
在另一个实施方案中，聚阳离子可具有下列一般结构：
Figure A20068003447900072
其中R是-CH3、-CH2CH3、-CH2CH2CH3、-(CH2)nCH3，X是Cl-、Br-、I-、F-、CO3 2-、SO4 2-、PO4 3-等。
具有上述式2的聚合物的实例包括但不限于聚(N-甲基-4-乙烯基吡啶碘化物)。
带负电的聚电解质(聚阴离子)可以为任何带负电聚合物。带负电聚合物的实例包括但不限于聚(苯乙烯磺酸钠)、聚丙烯酸钠盐、聚丙烯酸共聚物、聚(苯乙烯-共-苯乙烯磺酸钠)、聚(砜-共-磺酸钠)、聚(丙烯酸乙酯-共-丙烯酸钠)、聚(丁二烯-共-甲基丙烯酸锂)、聚(乙烯-共-甲基丙烯酸钠)、聚(乙烯-共-甲基丙烯酸镁)、锌-磺化乙烯-丙烯-三元共聚物、羧甲基纤维素钠盐、Nafion(Du Pont)、PFSI(Dow Chemical)。
在一个实施方案中，聚阴离子可具有下列一般结构：
其中M是Na+、Li+、K+、Zn2+、Mg2+、Al3+、Cu2+、Ag+、Ni2+等。
具有上述式3的聚合物的实例包括但不限于聚苯乙烯磺酸钠。
在另一个实施方案中，聚阴离子可以具有下列一般结构：
Figure A20068003447900082
其中M是Na+、Li+、K+、Zn2+、Mg2+、Al3+、Cu2+、Ag+、Ni2+等。
具有上述式4的聚合物的实例包括但不限于聚丙烯酸钠盐。
在进一步的实施方案中，可以向带正电的聚电解质溶液、带负电的聚电解质溶液或二者中加入添加剂(例如，中性聚合物)。这种添加剂可包括任何中性聚合物，例如，PVA、PEO、PVDF、PPO、PA、PEA、PEEK、PET、PMMA、聚(2，6-二甲基-1，4-苯撑氧)、聚(2，6-二苯基-1，4-苯撑氧)、聚(4-乙烯基吡啶)。特别的，可以使用PVA、PEO、PVDF及其它类似的聚合物。这种添加剂可掺入聚电解质中以改善性质，所述性质包括但不限于聚电解质膜的薄膜形成效果。
在其它实施方案中，可使用多孔基材(例如，无纺尼龙、聚丙烯(PP))或其它合适的基材。所述聚电解质膜涂布于基材的上部。
实施例
下列非限制性实施例描述了聚电解质膜的实施方案。
用5％聚(二烯丙基二甲基氯化铵)加3.5％PVA的溶液涂布无纺基材(例如，来自Freudenberg的FS2225)，以形成层A；用5％聚(苯乙烯磺酸钠)加3.5％PVA的溶液涂布所述无纺基材，作为层B。重复A与B二次，这样所得的膜具有BABABA的一般结构。因此，得到厚度为约0.1mm至约0.25mm的聚电解质膜。在45％KOH中，其导电性为10-1S/cm左右。
使用上述聚电解质膜，使用本发明描述的装置进行枝晶短路测试。与传统隔离件相比，本发明的聚电解质作为隔离件表现出较长的短路时问(参见表1)。
表1使用市售隔离件和聚电解质膜的枝晶测试
Figure A20068003447900091
枝晶短路测试如图2所示。在该装置中，使用Ni-海绵与Zn-板作为充电电极。测试膜夹置于PP隔离件之间，且通过后支撑体上的衬垫(washer)来控制距离。刚性后支撑体用于固定该装置的距离，并使用螺丝紧密支撑该装置。在锌枝晶短路测试期间，使用45％KOH+6％ZnO的电解液。Zn-电极具有3cm×3cm的尺寸，并使用1A恒定电流充电。记录短路时间，表1中列出了一些典型的短路数据。
使用本发明的聚电解质作为隔离件，枝晶短路测试的时间延长，如表1所示。枝晶短路时间越长，对于可充电电池而言越好，从而提供较长的循环寿命，通过使用所述聚电解质膜，预期可以获得较高循环数的可充电电池。
虽然已显示并描述了优选实施方案，但可在不偏离本发明的精神与范围下进行各种变化和取代。因此，应当理解，本发明通过示例说明，但没有限制。

Claims (16)

1.用于电化学电池的膜，其包含：
至少一对带相反电荷的膜，所述膜包括聚阴离子膜和邻近的聚阳离子膜，其中在所述聚阴离子膜与聚阳离子膜的界面处形成双电层。
2.电化学电池，其包含权利要求1的膜。
3.权利要求1所述的膜，其中彼此邻近地设置多对带相反电荷的膜。
4.权利要求1所述的膜，其中所述聚阴离子膜或聚阳离子膜中至少一个包括中性聚合物。
5.权利要求1所述的膜，其中形成所述聚阴离子膜的阴离子聚合物选自：聚(苯乙烯磺酸钠)、聚丙烯酸钠盐、聚丙烯酸共聚物、聚(苯乙烯-共-苯乙烯磺酸钠)、聚(砜-共-磺酸钠)、聚(丙烯酸乙酯-共-丙烯酸钠)、聚(丁二烯-共-甲基丙烯酸锂)、聚(乙烯-共-甲基丙烯酸钠)、聚(乙烯-共-甲基丙烯酸镁)、锌-磺化乙烯-丙烯-三元共聚物、羧甲基纤维素钠盐、Nafion及其它合适的聚阴离子。
6.权利要求1所述的膜，其中形成所述聚阴离子膜的阴离子聚合物具有下列结构：
其中M选自Na+、Li+、K+、Zn2+、Mg2+、Al3+、Cu2+、Ag+、Ni2+。
7.权利要求1所述的膜，其中形成所述聚阴离子膜的阴离子聚合物具有下列结构：
Figure A20068003447900031
其中M选自Na+、Li+、K+、Zn2+、Mg2+、Al3+、Cu2+、Ag+、Ni2+。
8.权利要求1所述的膜，其中形成所述聚阳离子膜的阳离子聚合物选自：聚(二烯丙基二甲基氯化铵)、聚(N-甲基-4-乙烯基吡啶碘化物)、聚(烯丙胺盐酸盐)、聚(丙烯酸丁酯-共-N-甲基-4-乙烯基吡啶碘化物)、聚(丁二烯-共-N-甲基-4-乙烯基吡啶)碘化物、聚(苯乙烯-共-4-乙烯基吡啶)、聚(丙烯酸乙酯-共-4-乙烯基吡啶)、聚苯胺基聚合物、聚吡咯基聚合物及其它合适的聚阳离子。
9.权利要求1所述的膜，其中形成所述聚阳离子膜的阳离子聚合物具有下列结构：
其中R1选自-CH3、-CH2CH3、-CH2CH2CH3、-(CH2)nCH3，R2选自-CH3、-CH2CH3、-CH2CH2CH3、-(CH2)nCH3，X是Cl-、Br-、I-、F-、CO3 2-、SO4 2-、PO4 3-。
10.权利要求1所述的膜，其中形成所述聚阳离子膜的阳离子聚合物具有下列结构：
Figure A20068003447900041
其中R选自-CH3、-CH2CH3、-CH2CH2CH3、-(CH2)nCH3，X是C1-、Br-、I-、F-、CO3 2-、SO4 2-、PO4 3-。
11.权利要求4所述的膜，其中所述中性聚合物选自PVA、PEO、PVDF、PPO、PA、PEA、PEEK、PET、PMMA、聚(2，6-二甲基-1，4-苯撑氧)、聚(2，6-二苯基-1，4-苯撑氧)及聚(4-乙烯基吡啶)。
12.权利要求1-11任一项所述的膜，其中所述聚阴离子膜与聚阳离子膜形成于基材上。
13.权利要求12所述的膜，其中所述基材为多孔基材。
14.权利要求13所述的膜，其中所述多孔基材包含尼龙或聚丙烯。
15.权利要求1-14任一项所述的膜，其中所述电化学电池包含二次电池，且所述膜保护二次电池免于发生枝晶相关的失效。
16.权利要求1-14任一项所述的膜，其中所述电化学电池包含直接燃料供给燃料电池，且所述膜保护直接燃料供给燃料电池免于发生燃料穿透。
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