CN1326596A - 聚合物基氢氧化物导电膜 - Google Patents
聚合物基氢氧化物导电膜 Download PDFInfo
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Abstract
本发明涉及一种聚合物基电解液组合物,该组合物具有极好的成膜性、柔韧性、机械强度和较高的氢氧根电导率。该组合物包括:一种含有烷基季铵盐结构的有机聚合物;一种含氮的杂环季铵盐;和一种金属氢氧化物。在优选的实施方案中,该组合物注塑成膜形,以适合于在燃料电池或碱性电池组等电源中用作离子导电膜或其它专用膜,所说的电源的运转是基于氢氧阴离子的转移。
Description
发明的领域
一般来讲,本发明涉及固体电解液(solid electrolyte)组合物,更具体地讲,本发明涉及一种聚合物基电解液组合物(polymer-based electrolytecomposition),其具有良好的成膜性、柔韧性、机械强度和高氢氧化物电导率(hydroxide conductivity)。
发明的背景
燃料电池直接由一种燃料源和一种氧化剂发电。燃料源可以是醇类、氢气、天然气或金属片等物质;而氧化剂可以是氧或空气等。由于该过程不“燃烧”燃料生热,热力学极限效率要比通常发电过程高得多。从原理讲,燃料电池是由被离子导电材料或膜分开的两个电极组成。这种离子导电膜必须允许离子由一个电极向另一个电极扩散,并且同时防止电子流穿过该膜,并将燃料和氧化剂成份分开。如果电子能穿过该膜,燃料电池将全部或部分短路,已经产生的任何有用的电能将消失或减少。燃料或氧化剂通过膜扩散或泄漏,也能导致不希望的后果。
早期的燃料电池装有液态电解液,例如酸、碱或盐等溶液作为离子导电物质。然而,随着技术用的进步,人们的兴趣已经转移到开发固体电解液离子导电膜,如固体质子交换膜、杜邦公司的Nafion(高氟化离子交换树脂)。与液体电解液组合物相比,固体电解液膜(solidelectrolyte membrane)有许多优点,例如,固体电解液燃料电池不含有任何腐蚀性物质或可以和密封材料或燃料电池容器的其它部分发生反应的溶剂。此外,采用固体电解液膜,燃料电池可以做的薄而轻,能将几组电池装配在一起。已经开发成功具有良好成膜性的电解液组合物,这种膜还具有优良的柔韧性、机械强度和高电导率。
固体电解液大体上可分成有机和无机两类。有机电解液典型的特点是离子电导率较低,但机械性能和柔韧性优良,并且可做成薄膜。而另一方面,无机固体电解液通常具有高离子电导率,但由于其晶体性质而机械强度不佳。
在过去20年中,对用于燃料电池和电池组等电化学设备的各种固体电解液组合物,进行了广泛地研究。例如,在1973年,P.V.Wright博士报告了用于锂离子电池组的一类固体电解液。这种电解液材料包括聚环氧乙烷((-CH2CH2O-)n)即PEO和一种锂盐。
Gray等在“以ABA嵌段共聚物为基体的新聚合物电解液”〖大分子,Macromolecules,21:392-397(1988)〗一文中,公开了一种苯乙烯一丁二烯一苯乙烯嵌段共聚物,其中离子导电体是短链PEO单甲醚与LiCF3SO3盐构成的络合物,该盐通过丁二酸与这种三元嵌段共聚物的丁二烯嵌段柔性连接体结合。
Stenzel在美国专利4,828,941中公开了一种聚合物基阴离子交换树脂固体电解液膜,该膜用于甲醇一空气燃料电池。
Takahashi等在美国专利5,643,490公开了一种聚合物固体电解液组合物,它包括一种含有烷基季铵盐结构的有机聚合物和一种冷熔盐(cold-melting salt)。该盐的成分是含氮杂环季铵盐和金属盐、优选卤化铝的反应产物。
其它聚合物基的固体电解液材料包括:PEO和碱金属盐例如钠盐的复合物;丙烯酸或甲基丙烯酸有机聚合物,其侧链含有PEO结构;聚膦腈有机聚合物,其主链为(-P=N-)、侧链为PEO结构;以及硅氧烷有机聚合物,其主链为(-SiO-),侧链含有PEO结构。这些聚合物基体材料尽管具有很高的离子电导率,但通常仅在非常高的温度下(100℃或更高)才起作用,因此不适用于室温下使用的一般的燃料电池或电池组。此外,这些材料的柔韧性和成膜性一般也不能满足需要。
随着最近H2/O2燃料电池的发展,人们把注意力集中到开发质子转移/交换膜上。例如,在70年代初,杜邦公司为了化学稳定性而引入全氟聚合物膜,即Nafion,此后它已成为质子交换膜燃料电池传统结构的基础。Nafion属于一类很广泛固体超强酸催化剂,其酸强度超过100%H2SO4的酸强度,其组成包括聚合物骨架中的疏水(-CF2-CF2-)区和亲水(-SO3H)区两部分,组合物的强酸性特点是全氟化碳链对磺酸基拉电子作用的结果。但是,Nafion生产成本很高,使得燃料电池的成本高到在商业上没有吸引力的水平。因此,人们已把注意力集中到开发廉价的质子导电材料上。
Ehrenberg等人在美国专利5,468,574中公开了一种质子导电膜,其包括多种酸稳定的聚合物分子,每一种至少含有一个离子导电组分,该离子导电组分以共价键连接到至少一个柔性连接成分上。这种膜的特征是高度磺化的聚合物膜,其组成为磺化聚苯乙烯、乙烯和丁烯嵌段的嵌段共聚物。
1997年,NASA′s喷气动力(Jet Propulsion)实验室公开了一种改进的质子导电膜,既可用于H2/O2燃料电池,也可直接用甲醇的燃料电池。这种膜材料的组成为高度磺化的聚醚醚酮(poly(ether ether ketone)),通常称为H-SPEEK。与以前的燃料电池膜材料相比,H-SPEEK声称在100~200。℃最佳操作温度范围中更稳定,甲醇的渗透性更低,并且生产成本低得多。参见“燃料电池用聚合物电解液膜材料”,NASA Tech Briefs,p.64,1997年9月。
当人们的注意力还继续集中在廉价质子导电燃料电池膜的开发上时,本发明者已经发现了另一类离子导电膜的重要性——一种转移氢氧离子的导电膜。氢氧离子的转移被认为是燃料电池和碱性电池组的电源运转基础。因此本发明者已经认识到,为了将有多种优点的固体电解液膜用到碱性电源中,需要提供具有良好成膜性包括柔韧性和机械强度的氢氧根导电膜组合物。所形成的膜必须允许氢氧阴离子扩散,并且同时防止电子流动以及气体分子扩散。此前已知的电解液组合物如碱金属离子交换膜和质子交换材料都不能满足这些标准,因此,不能作为氢氧根传导的固体电解液膜。
在本发明之前,碱性水溶液如氢氧化钾或氢氧化钠溶液,在燃料电池和碱性电池组中被用作液态电解液。电解液的作用是在电化学电池运转时,提供氢氧阴离子,以使离子从一个电极传导到另一个电极。认识到固体电解液膜的价值,本发明者已经发现了聚合物基电解液组合物,可以注塑成薄膜形,以取代燃料电池和碱性电池组中的液态电解液。
一种材料要在燃料电池和碱性电池组中起到固体电解液膜的作用,应当含有高密度的载氢氧离子(hydroxide carrierion);还应当含有能与载氢氧离子发生适当相互作用的官能团;甚至在低温(如室温)下也应保持非晶态;并且应当没有电子传导作用。本发明的聚合物基电解液组合物满足所有这些要求。
发明简述
本发明提供了一种聚合物基电解液组合物,包括一种含有烷基季铵盐阳离子结构的有机聚合物骨架;一种含氮的杂环铵盐;以及可以自一处向另一处自由转移的氢氧阴离子。更具体地讲,该组合物包括:(a)一种含有烷基季铵盐结构的有机聚合物;(b)一种含氮的杂环季铵盐;以及(c)一种金属氢氧化物,最好是氢氧化铝。
在一个实施方案中,本发明的聚合物基电解液组合物可以注塑成膜形。由于该组合物具有较高的氢氧根电导率,这种膜适于用作固体电解液膜,例如用作燃料电池中的固体电解液膜。更具体地讲,这种膜适于用作碱性电池组中或燃料电池中的氢氧根导电膜。
上述组合物中含有烷基季铵盐结构成分的有机聚合物最好是选自下列通式A和通式C所表示的化合物中:其中:R选自直接的键、-C(O)O-和-C(O)NH-;m是1~3中的一个整数;n是1~4中的一个整数;X-是一个相配的阴离子(counter anion),优选选自Cl-、Br-和I-。其中:R2可以选自一个直接的键和CH2;R3和R4每一个都是一个低级烷基;n是一个整数;X-是一个相配的阴离子,优选选自Cl-、Br-和I-。
含氮杂环季铵盐优选从烷基咪唑翁盐和烷基吡啶翁盐中选择。更优选的是,烷基吡啶翁盐为甲基和丁基吡啶翁盐,如碘化丁基吡啶翁(butylpyridinium iodide)。
在本发明的另一个实施方案中,上述组合物还进一步包含一种粘合剂,其作用是增加该组合物所制备膜的机械强度。
本发明的原理也提供了一种生产聚合物固体电解液膜的方法。该方法包括下列步骤:(a)将含有烷基季铵盐结构的有机聚合物、含氮的杂环铵盐和金属氢氧化物溶解于有机溶剂中制成溶液;以及(b)将得到的溶液注塑制成固体膜。上述有机溶剂最好从水、硝基甲烷或低级醇中选择。
在该方法的一个实施方案中,步骤(a)的进一步特征为该溶液还包含一种粘合剂;而在另一个实施方案中,步骤(b)的进一步特征为步骤(a)的溶液注塑到聚酯网中。因此,按照本发明的这些实施方案得到的膜,其拉伸强度得到了提高。
从下列优选实施方案的详细说明、附图和权利要求书中,将更加清楚地了解本发明的许多其它优点和特征。
附图的简单说明
图1是各种水性电解液得到的电压/电流密度曲线图;
图2是离子交换树脂Amberlite(OH)TM各种水溶液的氢氧根电导率。
图3是实施例3制备的电池所得到的电压/电流密度曲线图。
优选实施方案的详细说明
虽然本发明的实施方案可以有许多不同形式,但此处给出了一些优选的实施方案。不过,应该明白此处的公开只是用于对本发明进行说明,而不是将本发明限制在这些所述的实施方案中。
在一个实施方案中,本发明提供了一种聚合物基电解液组合物,包括:(a)含有烷基季铵盐结构的有机聚合物;(b)含氮的杂环铵盐;以及(c)氢氧阴离子源。在一个优选实施方案中,组合物的形式为适于用作离子导电固体电解液膜。这种膜可以用于电源中如燃料电池中。更具体地讲,这种膜适于用作燃料电池和碱性电池组中氢氧根导电固体电解液膜。
作为第一个组成成分,本发明的组合物包括一种含有烷基季铵盐结构的有机聚合物。尽管本发明没有定义该有机聚合物骨架的特定结构,但优选的聚合物结构是在聚合物侧链的端部含有烷基季铵盐基团的结构,以下列通式A为例说明:其中:R选自直接的键、-C(O)O-和-C(O)NH-中;m是1~3中的一个整数;n是1~4中的一个整数;X-是一个相配的阴离子(counteranion),优选选自Cl-、Br-和I-中。
通式A代表的有机聚合物可以用下述方法得到,例如:由包含烷基季铵盐结构的乙烯基单体制得的均聚物;或者由这些乙烯基单体和其它乙烯基共聚单体共聚而成。通式B所代表的共聚物可以由乙烯基单体和乙烯基共聚单体共聚制得。式中:U是一种由共聚的乙烯基共聚单体所得聚合物的结构单元;R选自直接的键、-C(O)O-和-C(O)NH-中;m是1~3中的一个整数:n是1~4中的一个整数;X-是一个相配的阴离子(counter anion),优选选自Cl-、Br-和I-中。
优选地,提供聚合物结构单元U的乙烯基共聚单体是含有乙烯基的不饱和烃。例如这些乙烯基共聚单体包括但不限于:丙烯酸类单体,如CH2=CHCOOH和CH2CHCOOR,其中,R是烷基;甲基丙烯酸类单体,例如CH2=CCH3COOH和CH2=CCH3COOR,其中R是烷基;CH2=[COO(CH2CH2O)nCH3]2,其中n是1~23中的一个整数;CH2=CH(C6H5);CH2=CHCN;CH2=CHCONH2;氯乙烯、乙烯基吡啶等等。共聚物可用一种或多种这些乙烯基共聚单体通过任何已知的方法共聚而得,例如自由基聚合法、光聚合法等等。
除了式A表示的有机聚合物外,本发明组合物中有机聚合物成分也包括这样的单体结构单元,其中,烷基季铵盐结构键合到聚合物主链上而形成环状结构,如下列通式C所表示的:R2可以选自一个直接的键和CH2;R3和R4每一个都是一个低级烷基;n是一个整数;X-是一个相配的阴离子,优选选自Cl-、Br-和I-。
式C表示的有机聚合物可用卤化二烯丙基二烷基铵单体(diallyldialkyl ammonium halide)聚合得到,或者由商业渠道购买。例如,聚氯化二烯丙基二甲铵可以用氯化二烯丙基二甲铵单体聚合得到。在本发明的优选实施方案中,通式C表示的有机聚合物平均分子量为20,000~500,000。
作为第二个组成成分,本发明的聚合物基电解液组合物包含一种含氮的杂环季铵盐。优选地,该组分为烷基咪唑翁盐或烷基吡啶翁盐。更优选的是烷基吡啶翁盐为甲基或丁基吡啶翁盐。该盐中相配的阴离子是从Cl-、Br-和I-等卤化物中选择。
作为第三个组成成分,本发明的聚合物基电解液组合物包含一个氢氧离子源。该氢氧离子源优选是一种氢氧化物(hydroxide salt),更优选的是一种金属氢氧化物(metal hydroxide salt),最优选的是氢氧化铝。
不限于任何特殊的理论,可以认为本发明的聚合物基电解液组合物中,氢氧根成分与有机聚合物中烷基季铵盐或含氮的杂环季铵化合物的相配阴离子形成络合物。可以进一步认为,在一个公用的相配阴离子上形成了准四面体结构的络合物和双准四面体结构的络合物,这取决于三种组成成分的比例。例如,当氢氧根成分是氢氧化铝时,可以形成[AlX(OH)3]-和Al2X(OH)6]-。
有机聚合物、含氮的杂环季铵盐和金属氢氧化物之间优选的比例范围取决于所用的有机聚合物和铵盐的种类。一般来讲,优选的比例范围为:每一摩尔的有机聚合物,0.2~0.6摩尔的含氮杂环铵盐,0.3~0.5摩尔的氢氧根组分。
本发明的聚合物基电解液组合物可用任何普通方法生产,例如,将三种组成成分均匀溶解于适当的溶剂中。通常,该组合物以膜的形式加以利用,而该膜可以采取任何通用的方法制成,如注塑成膜。这里溶解三种组分的溶剂可以是水、硝基甲烷或低级醇;将用这种方法得到的溶液铺展到基板(substrate)上,使溶剂挥发,就可得到膜。
为提高根据本发明的原理制造膜的机械强度,上述组合物还可以包含一种粘合剂,例如,丙烯酸、聚乙烯等等。可以在该组合物最初制备时,将粘合剂与其它组分一起均匀分散。这种改进的膜与上面的三组份膜具有相同数量级的电导率(conductivity),而拉伸强度提高了。
在本发明的另一实施方案中,例如将组合物注塑到聚酯网(polyestermesh)上而提高了所得到膜的机械强度。
按本发明的原理制备的、由组合物形成的聚合物基电解液膜可以用多种聚合物分子来表征,这些分子的每一种含有至少一种氢氧根导电成分,该导电成分以共价键至少与一种柔性、橡胶状连接成分结合。这些氢氧根导电成分如此排列,使得众多的连续的氢氧根导电通道穿过膜中,从第一面穿透到第二面,并且使这些通道位于由柔性连接成分形成的弹性基体中。在一优选的实施方案中,在这种膜的平面中,氢氧根导电通道的截面尺寸约为0.1mm。
根据本发明的原理,具有上述结构的固体电解液膜可以作为锌空气电池的固体电解液膜,如Faris等在美国专利5,250,370中所述。这种膜提供了自阴极向阳极传送电子的氢氧离子,从而在电池中形成电流。
下列的实施例更详细地说明了本发明的优选实施方案,但它们只是用于进行说明的,而不是以此来限制本发明。
实施例
实施例1.对燃料电池或碱性电池组中具有氢氧根导电功能材料的的早期研究中,本发明者是以氢氧化四烷基铵(tetraalkylammoniumhydroxide)溶液代替氢氧化钠或氢氧化钾电解液。选择氢氧化四烷基铵有两个理由:它提供了电化学电池运转所必须的氢氧阴离子;并且,它是聚合物主链上的一个侧链,不能自由迁移。随后的初步研究确立了氢氧化四甲铵水溶液和氢氧化四乙铵水溶液均可作为锌空气电化学电池的电解液。
图1是用40%氢氧化钾溶液或20%氢氧化四甲铵溶液为电解液的、锌空气电池中的电压/电流密度曲线。尽管使用氢氧化四甲铵溶液的电池在给定电流密度下电压较低(该结果不会令人惊奇,因为它没有提供象氢氧化钾那样高的氢氧阴离子浓度),本研究却强烈地表明,由氢氧化四甲铵溶液得到的氢氧阴离子,在燃料电池或碱性电池组运转中,可以担负在电极之间转移离子的作用。类似的试验表明,氢氧化四乙铵水溶液也有转移离子的功能。
实施例2在另一个初步研究模型中,将离子交换树脂Amberlite(OH)TM(美国费城罗姆-哈斯公司产)悬浮于去离子水中,测定氢氧阴离子的电导率随Amberlite(OH)TM重量百分数增加的变化。Amberlite(OH)TM是一种在其侧链上带有烷基季铵盐结构和氢氧化合物的有机聚合物。
图2表示的研究结果表明,随着去离子水中Amberlite(OH)TM浓度的增加,离子电导率(归因于OH-)迅速提高。当Amberlite(OH)TM浓度达50%时,溶液中氢氧阴离子的电导率为10-3S/cm数量级。该模型研究强烈表明,在其侧链上含有烷基季铵盐结构的有机聚合物,具有显著的OH-电导率;而且,由于Amberlite(OH)TM聚合物悬浮在水中,离子电导率也反映了OH-离子由固相到水相的转移,这是对固体电解液膜的另一项要求。
实施例3根据本发明的原理,将下列组分一起混合到一种适当的溶剂中,制成聚合物基电解液组合物:(a)一种含有烷基季铵盐结构的有机聚合物,即聚氯化二烯丙基二甲铵(poly(dially-dimethyl-ammonium)chloride,Aldrich化学公司制造,美国,WI,Milwaukee);(b)一种含氮的杂环铵盐,即碘化丁基吡啶翁;以及(c)一种氢氧阴离子源,即氢氧化铝。混合后,除去溶剂,得到固体样的灰白色(off-white)混合物,然后注塑成厚度为0.2mm的灰白色薄膜。
依下述方式测定实施例3得到的聚合物基固体电解液膜的离子电导率。在锌空气电池上加上一块5cm×5cm的该聚合物固体电解液膜,将该膜夹在锌片和空气扩散阴极之间。电化学电池保持在室温,并控制湿度确保电极和膜密切接触。用恒压、复合阻抗法得到电池的半圆形部分曲线,然后根据半圆形部分曲线解析计算电池的电导率。测得的该膜的电导率约为10-3S/cm数量级。
图3是实施例3所得电池的电压/电流密度曲线。由图上可以看到,在电流密度为10mA/cm2时,得到的电压是0.8伏。
本发明已用特定的实施方案详细地予以描述。但应该理解,这些实施方案只是用来进行说明,而不是仅限于此。很明显,根据本公开本领域的熟练人员可在权利要求书的精神和范围内进行改进和变化。
Claims (18)
1.一种聚合物基电解液组合物,包括:
一种含有烷基季铵盐结构的有机聚合物;
一种含氮的杂环季铵盐;以及
一种金属氢氧化物。
2.一种如权利要求1所述的聚合物基电解液组合物,其中,含有烷基季铵盐结构的有机聚合物具有通式A的结构:其中:R选自直接的键、-C(O)O-和-C(O)NH-;m是1~3中的一个整数;n是1~4中的一个整数;以及X-是一个相配的阴离子。
3.一种如权利要求2所述的聚合物基电解液组合物,其中,X-选自Cl-、Br-和I-中。
5.一种如权利要求4所述的聚合物基电解液组合物,其中,X-选自Cl-、Br-和I-中。
6.一种如权利要求1所述的聚合物基电解液组合物,其中,所述的含氮的杂环季铵盐选自烷基咪唑翁盐或烷基吡啶翁盐。
7.一种如权利要求6所述的聚合物基电解液组合物,其中,烷基吡啶翁盐选自甲基和丁基吡啶翁盐。
8.一种如权利要求7所述的聚合物基电解液组合物,其中,所述的丁基吡啶翁盐是碘化丁基吡啶翁。
9.一种如权利要求1所述的聚合物基电解液组合物,其中,所述的金属氢氧化物是氢氧化铝。
10.一种如权利要求1所述的聚合物基电解液组合物,包括:聚氯化二烯丙基二甲基铵、碘化丁基吡啶翁以及氢氧化铝。
11.一种如权利要求1所述的聚合物基电解液组合物,其中还含有粘合剂。
12.一种如权利要求1所述的聚合物基电解液组合物,其中,相对于每一摩尔的有机聚合物组分,所述的组合物中含有0.2~0.6摩尔的含氮的杂环铵盐组分以及0.3~0.5摩尔的氢氧化物组分。
13.一种生产聚合物基固体电解液膜的方法,包括下列步骤:
(a)将含有烷基季铵盐结构的有机聚合物、含氮的杂环铵盐以及金属氢氧化物溶解在一种有机溶剂中,制得溶液;以及
(b)将得到的溶液注塑,制成聚合物基固体电解液膜。
14.如权利要求13所述的方法,其中,有机溶剂选自水、硝基甲烷和低级醇中。
15.如权利要求13所述的方法,其中,所述的溶液制备步骤(a)还包括将一种粘合剂溶解于其中。
16.如权利要求13所述的方法,其中,所述的步骤(b)的特征为将得到的溶液注塑到聚酯网中。
17.如权利要求13所述的方法,其中,所述的步骤(a)包括将聚氯化二烯丙基二甲基铵、碘化丁基吡啶翁以及氢氧化铝溶解于有机溶剂中。
18.一种制备聚合物固体电解液膜的方法,包括下列步骤:
(a)将聚氯化二烯丙基二甲基铵、碘化丁基吡啶翁以及氢氧化铝溶解于有机溶剂中制成溶液;以及
(b)注塑所得到的溶液,以生成聚合物固体电解液膜。
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US09/156,135 | 1998-09-17 | ||
US09/156,135 US6183914B1 (en) | 1998-09-17 | 1998-09-17 | Polymer-based hydroxide conducting membranes |
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EP (1) | EP1116291A1 (zh) |
JP (1) | JP2002525803A (zh) |
KR (1) | KR20020020871A (zh) |
CN (1) | CN1174510C (zh) |
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BR (1) | BR9913832A (zh) |
CA (1) | CA2344148A1 (zh) |
HK (1) | HK1042594A1 (zh) |
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Also Published As
Publication number | Publication date |
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CN1174510C (zh) | 2004-11-03 |
AU6137299A (en) | 2000-04-03 |
HK1042594A1 (en) | 2002-08-16 |
US6183914B1 (en) | 2001-02-06 |
JP2002525803A (ja) | 2002-08-13 |
AU743088B2 (en) | 2002-01-17 |
KR20020020871A (ko) | 2002-03-16 |
EP1116291A1 (en) | 2001-07-18 |
MXPA01002831A (es) | 2002-04-08 |
TW463413B (en) | 2001-11-11 |
CA2344148A1 (en) | 2000-03-23 |
BR9913832A (pt) | 2001-12-18 |
WO2000016422A1 (en) | 2000-03-23 |
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