CN117397071A - 质子交换膜状物 - Google Patents
质子交换膜状物 Download PDFInfo
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- CN117397071A CN117397071A CN202280038726.7A CN202280038726A CN117397071A CN 117397071 A CN117397071 A CN 117397071A CN 202280038726 A CN202280038726 A CN 202280038726A CN 117397071 A CN117397071 A CN 117397071A
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- vinylidene fluoride
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Abstract
本发明涉及质子交换膜状物、制备所述膜状物的方法以及所述膜状物在需要离子交换的领域(诸如污水净化和电化学或能量领域)中的用途。特别地,这种膜状物被用于燃料电池膜状物的设计中。
Description
技术领域
本发明涉及质子交换膜状物、制备所述膜状物的方法以及所述膜状物在需要离子交换的领域(诸如电化学或能量领域)中的应用。特别地,该膜状物用于燃料电池膜状物的设计中,诸如用于H2/空气或H2/O2燃料电池(这些电池称作“质子交换膜状物燃料电池”,缩写PEMFC)或甲醇/空气燃料电池(这些电池称作“直接甲醇燃料电池”,缩写DMFC)的质子传导膜状物。
背景技术
燃料电池是电化学发生器,其在氧化剂的存在下将燃料氧化反应的化学能转化成电能、热和水。通常,燃料电池包括多个串联安装的电化学电池,每个电池包括通过充当固体电解质的质子交换膜状物分开的极性相反的两个电极。所述膜状物允许在燃料在阳极处氧化期间形成的质子向阴极传递。
所述膜状物构成燃料电池的核,并且它们因此必须具有良好的质子传导性能以及对反应性气体(对于PEMFC燃料电池,为H2/空气或H2/O2;对于DMFC燃料电池,为甲醇/空气)的低透过性。构成所述膜状物的材料的性质基本上是热稳定性、耐水解性和耐氧化性,以及一定程度的机械柔韧性。
通常使用并满足这些要求的膜状物是由例如属于聚砜、聚醚酮、聚苯和聚苯并咪唑家族的聚合物获得的膜状物。然而,已经发现这些非氟化聚合物在燃料电池环境中相对快速地降解,并且它们的使用寿命暂时不足以用于PEMFC应用。
大多数质子交换膜状物都是基于全氟化聚合物化学,所述全氟化聚合物具有带有磺酸官能团的长或短分支。除了它们的高成本之外,这些各种聚合物具有低的对氢氧根自由基的耐受性(这限制了它们在燃料电池环境中的耐久性),和低的机械强度。此外,这些膜状物具有离子传导性/氢透过性比率,该比率使得不能够获得结合了高不透过性和高传导性的薄膜状物。此外,全氟化膜状物具有不允许它们在80℃以上的温度下长时间运行的温度使用限制。
为了在80℃以上的温度下获得在质子传导方面的长期效益,一些作者提出了更复杂的材料,该材料除了聚合物基质外,还包含质子传导粒子,因此导电性不再仅仅归因于构成膜状物的聚合物。申请WO 2014/173885就是这种情况,它描述了包含聚合物基质和由无机离子交换粒子组成的填料的复合材料,所述粒子在氟化聚合物基质内原位合成。这些膜状物表现出无机粒子在聚合物基质内的更均匀分布。然而,这种类型的膜状物具有与单独由聚合物基质制成的膜状物相比的较低机械性质、由于燃料电池运行期间尺寸的变化而在粒子-基质界面处有气穴的风险,并且难以在工业规模上制造。
通过辐射诱导的接枝所生产的离子传导膜状物是提高它们的化学稳定性的另一种选择。辐射诱导的接枝反应通过单体在膜中的扩散和单体聚合反应来控制。反应从经辐照的膜的表面处开始,并逐渐移动通过膜的主体。已经描述了基于乙烯-四氟乙烯(ETFE)、氟化乙烯-丙烯(FEP)和乙烯-氯三氟乙烯(ECTFE)的膜,特别是对于两性离子交换膜状物。
确实需要具有改善的性质、特别是改善的耐热性和更高的传导性/气体透过性比率的质子交换膜状物。
发明内容
为了克服上述缺点,本发明人开发了状物,该膜状物具有从偏二氟乙烯基共聚物开始获得的非常特殊的形态。
根据第一方面,本发明涉及质子交换聚合物电解质膜状物,所述膜状物由其上接枝有苯乙烯类单体和腈类单体的经辐照的偏二氟乙烯(VDF)共聚物基膜组成,所述基膜带有共价键合到VDF共聚物上的质子交换磺酸根基团。
该VDF共聚物首先通过本领域技术人员已知的任何技术转化为膜形式:挤出吹塑、平膜挤出,但也有例如通过溶剂浇铸(流延)的膜生产。由此获得的膜具有共连续形态,具有可含有至多10%的共聚单体的富含VDF的高度结晶的相和含有超过5%的共聚单体至至多35%的共聚单体的基于VDF共聚物的无定形或准无定形相。
根据第二方面,本发明涉及生产质子交换聚合物电解质膜状物的方法,所述方法包括用苯乙烯类和腈类单体的混合物接枝经辐照的VDF共聚物膜,随后通过磺化对如此辐照和接枝的膜进行后处理。
根据另一方面,本发明涉及质子交换聚合物电解质膜状物在以下领域中的应用:
-燃料电池,例如H2/空气或H2/O2燃料电池或甲醇/空气燃料电池;
-电解槽;
-锂电池,所述膜状物有可能是电解质的组成的一部分。
本发明使得克服现有技术的缺点成为可能。更具体地,它提供一种使得以下成为可能的技术:
-针对低于140℃的温度,提高膜在无流动的情况下的耐热性(热阻);
-提高与商业NAFION型膜状物相比的对氢氧根自由基的耐受性;
-提高与现有技术相比的传导性/氢透过性比率。
具体实施方式
现在将在以下描述中以非限制性方式更详细地描述本发明。
根据第一方面,本发明涉及一种质子交换聚合物电解质膜状物,所述膜状物由其上通过辐照接枝有苯乙烯类单体和腈类单体的偏二氟乙烯共聚物基膜组成,所述膜带有共价键合到VDF共聚物上的质子交换磺酸根基团,所述共聚物具有共连续型的非均相结构。
根据各种实施方案,所述电极包括在适当的情况下结合的以下特征。除非另外指出,否则所示含量均以重量表示。
根据一个实施方案,苯乙烯类单体/腈类单体摩尔比范围为0.7至1.3。
根据一个实施方案,本发明的偏二氟乙烯共聚物是可熔融转化的非均相热塑性共聚物,并且包含两个或更多个共连续相,所述共连续相包含:
a)25重量%至50重量%的第一共连续相,其包含90重量%至100重量%的偏二氟乙烯单体单元和0重量%至10重量%的至少一种另外的含氟单体单元,和
b)大于50重量%至75重量%的第二共连续相,其包含65重量%至95重量%的偏二氟乙烯单体单元和一种或多种选自六氟丙烯和全氟(乙烯基醚)的共聚单体,以引起第二共连续相与第一共连续相的相分离。
所述非均相共聚物含有在固体状态下产生共连续结构的两个或更多个相。共连续相彼此不同,并且可以用扫描电子显微镜(SEM)观察。根据本发明的非均相共聚物不同于包含单相的均相共聚物。
第一共连续相富含偏二氟乙烯单体单元,含有至少90重量%、并且优选至少98重量%的偏二氟乙烯单体单元。在一个实施方案中,第一共连续相是聚偏二氟乙烯(PVDF)均聚物。
如果第一共连续相是共聚物,则它可以由选自以下的一种或多种另外的氟化单体形成:六氟丙烯、四氟乙烯、三氟乙烯、氯三氟乙烯、氟乙烯、五氟丙烯、全氟(甲基乙烯基醚)和全氟(丙基乙烯基醚)。
如果该共聚单体与第二共连续相中的主要共聚单体相同,那么不超过10%的该共聚单体可以存在于第一共连续相中,因为在所述相中的聚合物必须是足够不同的以便形成在热力学上为分离的相。在一个实施方案中,在第一和第二相的共聚物之间的共同共聚单体的水平的差异应该为至少10%(绝对值)。
含有共聚物的第二相将与该第一相在热力学上为分离的以形成具有共连续结构的非均相组合物。该共聚物含有有效量的选自六氟丙烯(HFP)和全氟烷基醚(PAVE)、氯三氟乙烯(CTFE)、三氟乙烯的共聚单体,与大多数(大于50重量%)的偏二氟乙烯单体单元。优选地,第二共连续相含有至少1重量%的HFP或PAVE。该共聚物还可以含有可与VDF共聚的另外的共聚单体。
共聚单体的有效量是允许该共聚物形成与该第一相不同的分开的相的量。当共聚单体是HFP时,第二相聚合物中的有效量为5重量%至35重量%、优选15重量%至33重量%、更优选26重量%至31重量%。在本发明中可用的全氟烷基醚是具有以下结构的那些:CF2=CF-O-Rf,其中Rf是选自-CF3、-CF2CF3和-CF2CF2CF3的一个或多个全氟烷基。优选的全氟烷基乙烯基醚是全氟(甲基乙烯基醚)。
基于所有单体的总量,共连续共聚物含有2.5重量%至31重量%、更优选大于2.5重量%至26重量%、更优选13重量%至23重量%的HFP和/或PAVE。
根据一个实施方案,所述膜状物由由偏二氟乙烯共聚物制成的基膜组成,基于共聚物的总重量,所述共聚物包含可含有至多10%的HFP的富含VDF的高度结晶的相和含有超过5%的HFP至至多35%的HFP的基于VDF-HFP共聚物的无定形相。
形成根据本发明的膜状物的基膜的非均相共聚物可以根据文献WO 2016/130413中描述的方法合成,该方法包括涉及以下的步骤:
a)向反应器中装入包含水、表面活性剂、偏二氟乙烯和引发剂的初始原料;
b)引发聚合;
c)向该反应器中引入包含偏二氟乙烯和引发剂的原料直到已向该反应器中引入了待在该反应中使用的偏二氟乙烯的总重量的25重量%至小于50重量%,以形成第一相聚合物;
d)以有效的量向该反应器中加入选自六氟丙烯和全氟烷基乙烯基醚的共聚单体,以使作为第二相共聚物形成的偏二氟乙烯共聚物与第一相聚合物相分离;
e)继续供应偏二氟乙烯和引发剂直到所有的偏二氟乙烯已经加入到该反应器中,以形成非均相、共连续的聚偏二氟乙烯共聚物组合物;和
f)从该反应器中取出该共连续的聚偏二氟乙烯共聚物组合物。
该共聚物通过本领域技术人员已知的任何技术转化为膜形式:挤出吹塑、平膜挤出,但也有例如通过溶剂浇铸的膜生产。
根据一个实施方案,膜具有5至150μm、并且优选地在15和120μm之间的厚度。
根据第二方面,本发明涉及生产质子交换聚合物电解质膜状物的方法,所述方法包括用苯乙烯和腈类单体的混合物对VDF共聚物膜进行辐照诱导的接枝,随后通过磺化对如此辐照和接枝的膜进行后处理。
根据一个实施方案,为了制备根据本发明的电解质膜状物,首先将上述基膜暴露于电离辐射以引入活性位点。通过电子束、伽马射线或X射线源以在25和150千戈瑞(kgray)之间、优选在50和125kg千戈瑞之间的剂量辐照膜。辐照在真空、空气或氮气下进行。然后将经辐照的基础聚合物暴露于包含苯乙烯类单体和腈类单体的单体混合物中。
根据一个实施方案,所述苯乙烯类单体为α-烷基苯乙烯型,其中烷基选自:甲基、乙基、丙基、丁基、戊基和己基。
根据一个实施方案,所述苯乙烯类单体选自:α-甲基苯乙烯、α-氟苯乙烯、α-溴苯乙烯、α-甲氧基苯乙烯和α,β,β-三氟苯乙烯。
根据一个实施方案,所述苯乙烯类单体是α-甲基苯乙烯(AMS)。
根据一个实施方案,所述腈类单体选自丙烯腈、2-甲基-2-丁烯腈、2-亚甲基戊二腈和甲基丙烯腈。
根据一个实施方案,在用异丙醇冲洗之前,将膜通入60℃的含有在30%和50%之间的α-甲基苯乙烯和在30%和50%之间的亚甲基戊二腈的异丙醇浴中。
根据一个实施方案,所述腈类单体是2-亚甲基戊二腈(MGN)。
根据一个实施方案,以上所述的基膜在包含所述苯乙烯类单体和所述腈类单体的单体混合物的存在下被辐照。通过电子束、伽马射线或X射线源以在25和150千戈瑞(kgray)之间、优选在50和125kg千戈瑞之间的剂量辐照膜。辐照是在真空、空气或氮气下进行的。
然后将经接枝的膜与氯磺酸进行后官能化反应,随后在水中或碱性溶液中水解。这使得阳离子交换-SO3H官能团能够被引入到膜上。
根据一个实施方案,然后用蒸馏水冲洗带有共价键合的-SO3H官能团的经接枝的膜,直到冲洗水具有中性pH,然后在80℃下水解,然后在空气中干燥。由此产生的膜的厚度和重量增加了30%至80%。
经由基于相对于PVDF参考峰的芳族基团的特定峰和/或腈基的特定峰的面积之间的比率的校准曲线,通过透射红外(IR)光谱的测量显示出按重量计在25%和55%之间、优选在35%和50%之间的接枝度。
有利地,电解质膜状物的离子交换容量(IEC)大于0.6mmol/g。IEC的测量如下:在搅拌下将1cm×1cm样品浸入0.5M的KCl溶液中过夜。溶液中存在的氢离子在与磺酸根基团上的K+交换后,之后用0.05M KOH溶液滴定至pH=7。然后根据以下方程式计算离子交换容量:
其中n(H+)是质子的摩尔数,W干是以其H+形式的干膜状物的重量,c(KOH)是KOH的浓度,V(KOH)是加入用于滴定的KOH溶液的体积,WK是以其K+形式的干膜状物的重量,并且M(K+)和M(H+)分别是K+和H+的摩尔质量。
有利地,根据一个实施方案,根据本发明的电解质膜状物的氢透过性小于2mA/cm2。为了该测量,将膜状物放置在燃料电池的腔室中,然后在阴极处施加氢气流,同时在阳极处施加氮气流。然后在两侧施加电势,并测量通过氢气传输通过膜状物而获得的电流。
有利地,根据一个实施方案,根据本发明的电解质膜状物的氢透过性小于2×10- 2mL/min.cm2。为了该测量,将膜状物放置在与气相色谱仪相连的渗透计的腔室中。用氦气吹扫渗透计腔室,然后在0.1MPa的压力下将氢气流施加到膜状物的上表面。然后通过气相色谱法测量扩散通过膜状物进入下部的氢气流。
-40℃和140℃之间的动态力学分析(DMA)表明膜状物不会熔化,这允许在比已知膜状物更高的温度下使用,尤其是在80℃以上的温度下使用。对于30μm的膜厚度,在23℃、50%相对湿度下以20mm/分钟的速度测量的其断裂伸长率大于100%。
根据另一方面,本发明涉及质子交换聚合物电解质膜状物在以下领域中的应用:
-燃料电池,例如H2/空气或H2/O2燃料电池或甲醇/空气燃料电池;
-电解槽;
-锂电池,所述膜状物有可能是电解质的组成的一部分。
根据一个实施方案,聚合物电解质膜状物旨在插入电极-膜状物-电极组件内的燃料电池装置中。
这些膜状物有利地为具有例如10至200微米的厚度的薄膜形式。
为了制备这样的组件,可以将膜状物放置在两个电极之间。然后在适当的温度下压制由布置在两个电极之间的膜状物形成的组件,以获得良好的电极-膜状物粘附性。
然后将电极-膜状物-电极组件放置在两个板之间,确保导电和向电极供应反应物。这些板通常被称为双极板。
Claims (11)
1.质子交换聚合物电解质膜状物,所述膜状物由其上接枝有苯乙烯类单体和腈类单体的经辐照的偏二氟乙烯共聚物基膜组成,所述基膜带有共价键合到VDF共聚物上的质子交换磺酸根基团,所述共聚物具有共连续型的非均相结构。
2.根据权利要求1所述的膜状物,其中所述偏二氟乙烯共聚物是可熔融转化的非均相热塑性共聚物,并且包含两个或更多个共连续相,所述共连续相包含:
a)25重量%至50重量%的第一共连续相,其包含90重量%至100重量%的偏二氟乙烯单体单元和0重量%至10重量%的至少一种另外的含氟单体单元,和
b)大于50重量%至75重量%的第二共连续相,其包含65重量%至95重量%的偏二氟乙烯单体单元和一种或多种选自六氟丙烯和全氟(乙烯基醚)的共聚单体,以引起所述第二共连续相与所述第一共连续相的相分离。
3.根据权利要求2所述的膜状物,其中所述第一共连续相包含至少90重量%、优选至少98重量%的偏二氟乙烯单体单元,和一种或多种选自以下的另外的氟化单体:六氟丙烯、四氟乙烯、三氟乙烯、氯三氟乙烯、氟乙烯、五氟丙烯、全氟(甲基乙烯基醚)和全氟(丙基乙烯基醚)。
4.根据权利要求2和3中任一项所述的膜状物,其中基于共聚物的总重量,所述共聚物包含可含有至多10%的HFP的富含VDF的高度结晶的相和含有超过5%的HFP至至多35%的HFP的基于VDF-HFP共聚物的无定形相。
5.根据权利要求1至4中的一项所述的膜状物,其中所述膜用α-甲基苯乙烯和2-亚甲基戊二腈接枝,并用氯磺酸官能化。
6.根据权利要求1至5中的一项所述的材料,其中苯乙烯类单体/腈类单体摩尔比范围为0.7至1.3。
7.根据权利要求1至6中的一项所述的膜状物,其具有小于2×10-2mL/min.cm2的氢透过性。
8.根据权利要求1至7中的一项所述的膜状物,其具有通过用0.05MKOH溶液滴定测量的大于0.6mmol/g的离子交换容量(IEC)。
9.生产权利要求1至8中的一项所述的质子交换聚合物电解质膜状物的方法,所述方法包括用苯乙烯类和腈类单体的混合物接枝所述经辐照的VDF共聚物膜,随后通过磺化对如此辐照和接枝的膜进行后处理。
10.根据权利要求9所述的方法,包括以下步骤:
-将所述膜暴露于选自电子束、伽马射线或X射线的电离辐射;
-将经辐照的膜暴露于单体的混合物,所述单体的混合物包含选自α-甲基苯乙烯、α-氟苯乙烯、α-溴苯乙烯、α-甲氧基苯乙烯和α,β,β-三氟苯乙烯的苯乙烯类单体,以及选自丙烯腈、2-甲基-2-丁烯腈、2-亚甲基戊二腈和甲基丙烯腈的腈类单体;
-使经接枝的膜与氯磺酸进行后官能化反应,随后在水中或碱性溶液中水解。
11.燃料电池,其包括根据权利要求1至8中任一项所述的膜状物。
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FRFR2105701 | 2021-05-31 | ||
FR2105701A FR3123508A1 (fr) | 2021-05-31 | 2021-05-31 | Membrane echangeuse de protons |
PCT/FR2022/051033 WO2022254144A1 (fr) | 2021-05-31 | 2022-05-31 | Membrane echangeuse de protons |
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FR3004717B1 (fr) | 2013-04-23 | 2015-04-24 | Commissariat Energie Atomique | Procede de preparation d'un materiau composite echangeur d'ions comprenant une matrice polymere specifique et une charge consistant en des particules echangeuses d'ions |
EP3054518A1 (en) * | 2015-02-06 | 2016-08-10 | Paul Scherrer Institut | Electrolyte membrane with selective ion transport properties and a redox flow battery comprising an electrolyte membrane |
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