CN102971900A - 质子传导膜的制造方法 - Google Patents
质子传导膜的制造方法 Download PDFInfo
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- CN102971900A CN102971900A CN2011800069590A CN201180006959A CN102971900A CN 102971900 A CN102971900 A CN 102971900A CN 2011800069590 A CN2011800069590 A CN 2011800069590A CN 201180006959 A CN201180006959 A CN 201180006959A CN 102971900 A CN102971900 A CN 102971900A
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Abstract
一种用于生产质子传导膜的方法,所述方法包括:混合(i)5体积%~60体积%的具有良好的酸吸附能力的非导电无机粉末,所述粉末包括基本纳米尺寸的粒子;(ii)5体积%~50体积%的聚合物粘合剂,其与酸、氧化剂和燃料是化学相容的;和(iii)10~90体积%的酸或酸的水溶液,其中所述混合在不同的速率步骤下进行,由此生产一种混合物;将所述混合物在环境温度下连续浇铸在卷绕的纸或非织造基质等上;将所述经浇铸的混合物在大于100℃的温度下干燥约5~30分钟,由此形成干膜;和将多个所述干膜在压力下层合在一起,并随后从所述干膜的孔隙中提取成孔剂,由此形成平均孔径小于30纳米的所述质子传导膜。
Description
背景技术
1.技术领域
本发明一般性涉及质子传导膜(PCM)例如含有无机陶瓷氧化物的复合聚合物膜的生产方法。
2.相关现有技术描述
质子传导膜(PCM)被用于许多电化学应用中,包括燃料电池、电解池、超级电容器、传感器和电池。Nafion是在接近室温(至多100℃)运行的燃料电池中最常用的膜。作为固体聚合物电解质的Nafion具有两个主要的缺点,即非常昂贵和在燃料电池运行期间由于水被质子拖曳而导致干燥。近年来,已经加强努力开发了低成本的固体聚合物电解质来取代Nafion,并取得了显著进展。在Emanuel Peled公开的一些论文和专利例如US6447943、US6492047中已经讨论了室温质子传导材料。此外,在例如US6811911、US6447943、US7413824和EP141045381中已知用于电化学应用的纳米多孔质子传导膜(NP-PCM),这些专利文件的全文通过引用并入本文。
发明内容
提供一种低成本、高效地制造高传导性PCM的新方法。在一个实施方案中,该方法以放大工艺实施。也就是说,在针对实际应用的燃料电池开发中最重要的关键挑战是通过使用具有可接受的寿命和性能的低成本组件来提高经济性。
一种用于生产质子传导膜的方法,该方法包括:混合(i)5体积%~60体积%的具有良好的酸吸附能力的非导电无机粉末,所述粉末包括基本纳米尺寸的粒子;(ii)5体积%~50体积%的聚合物粘合剂,其与酸、氧化剂和燃料是化学相容的;和(iii)10~90体积%的酸或酸的水溶液,其中所述混合在不同的速率步骤下进行,由此生产质子传导混合物;将所述质子传导混合物在环境温度下连续浇铸在卷绕的纸、非织造基质或任何其他可涂覆材料上;将该经浇铸的质子传导混合物在大于100℃的温度下干燥约5~60分钟,由此形成干膜;将多个所述干膜在压力下层合在一起,并随后从所述干膜的孔隙中提取成孔剂,由此形成平均孔径小于30nm的质子传导膜。
本发明公开的新型PCM包括具有良好的酸吸附能力的纳米陶瓷粉末、聚合物粘合剂以及吸附在纳米孔隙中的酸。该PCM在再生燃料电池(RFC)应用中特别有用。
该PCM的主要组分是聚合物粘合剂、无机纳米尺寸粉末和酸性溶液或酸。PCM孔的典型直径为约1.5~30nm,优选3nm。所述孔充填有游离酸分子,这对于使用酸性电解质的储能系统(例如,RFC应用)是一个主要优点。
不同于前述的PCM,本发明公开的试剂(即,粉末和溶剂)与改善溶液质量的添加剂混合并且得到浇铸膜的更好的机械和物理性质。随后,利用机械涂布机将该溶液浇铸,这是更有效的方法和更均匀的方法。
根据本发明公开的独特方法,将至少2~6个,优选4个干膜层合在一起。混合步骤的各种速率步骤包括:室温下以约100~500rpm的混合速率混合1~5小时;在约30℃~50℃的温度下以约400~700rpm的混合速率混合10~20小时;室温下以100~400rpm的混合速率混合10~20小时;和在约30℃~50℃的温度下脱气5~30分钟。连续浇铸质子传导混合物的步骤是使用涂布机将溶液施涂在卷绕的纸、非织造基质或类似的辊对辊载体支持物上。
载体支持物是硅化纸,并且载体支持物的滚动速度是根据质子传导混合物的比重进行设定的。
干膜的厚度为约40~60微米,更优选约50~55微米。
优选地,层合所述干膜的步骤在约5~20kg/cm2的压力和约130~150℃的温度下进行约3~10分钟。
质子传导膜的平均孔径小于3nm,更优选平均孔径小于1.5nm。
该方法还包括在混合之前添加至少一种流变控制剂。流变控制剂是选自:SPAN80(提供一般化学描述的山梨醇单油酸酯,C24H44O6)和FSN(提供一般化学描述的(C2H4O)x(CF2)yC2H5FO,非离子含氟表面活性剂)中的至少一种。
提取步骤包括:(a)将含有成孔剂的质子传导膜在乙醚/乙醇混合物中浸渍足以从所述质子传导膜的孔隙中移除所述成孔剂的时间段;(b)将来自步骤(a)的质子传导膜在乙醇中浸渍以消除任何残留的成孔剂和其他溶剂;以及(c)将所述质子传导膜在水中浸渍以从所述孔隙中移除乙醇。
乙醚/乙醇混合物具有约1∶9~3∶7的比例。浸渍步骤(a)进行约1~5小时。浸渍步骤(b)进行约1~5小时。
无机粉末是选自SiO2、ZrO2、B2O3、TiO2、Al2O3以及Ti、Al、B和Zr的氢氧化物和氧氢氧化物(oxy-hydroxide)中的至少一种粉末。
聚合物粘合剂是选自以下的至少一种粘合剂:聚偏二氟乙烯、聚偏二氟乙烯-六氟丙烯、聚四氟乙烯、聚甲基丙烯酸甲酯、聚磺酰胺、聚丙烯酰胺、聚氯乙烯、丙烯腈、聚氟乙烯和Kel FTM即三氟氯乙烯均聚物。
所述酸是选自以下的至少一种:多氟烯烃磺酸、全氟烯烃磺酸、多氟芳基磺酸、全氟芳基磺酸、至多50%的氢或氟原子被氯原子取代的酸、CF3(CF2)nSO3H、HO3S(CF2CH2)nSO3H、CF23(CF2CH2)nSO3H、HO3S(CF2)nSO3H,其中n是具有1~9的值的整数、NafionTM离聚体(即全氟磺酸-PTFE共聚物)、HCl、HBr、磷酸和硫酸。
多氟芳基磺酸是选自以下的至少一种:多氟苯磺酸、多氟甲苯磺酸和多氟苯乙烯磺酸。全氟芳基磺酸是选自以下的至少一种:全氟苯磺酸、全氟甲苯磺酸和全氟苯乙烯磺酸。
所述方法还包括选自以下的成孔剂:DBP(即邻苯二甲酸二丁酯)、邻苯二甲酸二乙酯、邻苯二甲酸二甲酯、碳酸亚丙酯、碳酸亚乙酯等或其任意组合。
该方法还包括重新捕获酸或酸的水溶液的步骤。
具体实施方式
选自RFC、燃料电池、电解池、电池、电化学传感器等的电化学装置使用各种类型的离子导电膜。
所公开的膜是共聚物基体(例如,由两种(或更多种)单体物质衍生的聚合物)、陶瓷粉末(例如,无机或非金属材料)的组合。大多数陶瓷是金属与非金属元素之间的化合物,其中的原子间键是完全离子的或主要是离子的,但具有一些共价性质,并且相容的有机溶剂增塑剂保持柔性自支持膜形式的均质组合物。
PCM的改进放大制造工艺包括使用大量的材料、更好地形成悬浮体的添加剂、专业的混合设备和工业涂布机,以下将详细说明。
该方法中的基本化学品是无机粉末例如陶瓷粉末,更特别的是,SiO2、ZrO2、B2O3、TiO2、Al2O3以及Ti、Al、B和Zr的氢氧化物和氧氢氧化物;以及高分子粘合剂如聚偏二氟乙烯(PVDF)等,它们在溶剂和添加剂的混合物中混合。混合物中的二氧化硅的体积百分比为5~50%,优选15~40%,更具体的范围是20~30%。膜通过以下方法利用在上述范围内的几种组合物制造。溶剂对固体之比小于10∶1,优选是4∶1以下。参见,US6811911,其全文通过引用并入本文。
如前所述,固体、溶剂和添加剂在具有特氟隆(Teflon)涂层搅拌器的大容量烧瓶(3~10升,优选5升)在不同的速度和温度下根据以下步骤混合。混合步骤如下所述:
1.单独预混合所有的液体物质和所有固体;
2.将固体分散在溶剂中,同时在交替的速度和温度下搅拌几个小时;
3.所得溶液准备好浇铸,并且可以在密闭容器中贮存几个星期。
前面讨论的技术使用手工涂布器或半自动涂布器(如RK印刷或类似装置的K控制涂布器),其易于变动和不一致。与上述方法不同的是,在本实施方案中利用采用“Doctor Knife”方法的涂布试验机来进行膜的浇铸,如在通过引用全文并入本文的美国专利US4119836中所述的,易于在适当连续的“辊对辊”支持物上进行溶液施涂。所用的载体支持物可以是硅化纸、织物、非织造碳支持物或由其容易地制成膜的任何其他支持物,并且机器中纸的滚动速度根据溶液参数(比重、粘度等)来设定。根据溶液性质调节刀间隙以满足所需的膜厚,并且将溶液连续涂覆在纸上,同时滚动进入退火烘箱。烘箱的前部温度为90~110℃。在烘箱中的总停留时间由滚动速度和膜厚来确定。
质子传导膜
优选的固体电解质膜是质子传导膜,其具有直径尺寸基本小于30nm的孔隙并且包含:(i)5~60体积%的具有良好的酸吸附能力的非导电无机粉末,所述粉末基本上包含纳米粒子;(ii)5~50体积%的聚合物粘合剂,其与酸、氧和所述燃料是化学相容的;和(iii)10~90体积%的酸或酸的水溶液。
用于燃料电池的固体质子传导膜描述在美国专利6447943和6492047中,它们的全文通过引用并入本文。在这些膜中使用的聚合物粘合剂选自聚偏二氟乙烯、聚偏二氟乙烯-六氟丙烯、聚四氟乙烯、聚甲基丙烯酸甲酯、聚磺酰胺、聚丙烯酰胺、聚氯乙烯、丙烯腈、聚氟乙烯和Kel FTM及其任意组合。
用于制备固体质子传导膜的无机纳米粉末选自SiO2、ZrO2、B2O3、TiO2、Al2O3以及Ti、Al、B和Zr的氢氧化物和氧氢氧化物及其任意组合。
本发明的用于燃料电池的质子传导膜还包含酸。例如,与例如在美国专利5599638(其全文通过引用并入本文)中描述的其中不存在游离酸的固体电解质膜相反,本文所讨论的固体电解质膜在用于燃料电池中时,含有被捕获在膜的孔隙内的游离酸。作为替代方案,可含有与无机粉末键合的酸分子。这些孔隙的典型直径基本小于30nm,优选小于20nm,更优选小于3nm。
与电池硬件和两个电极处的催化剂相容的大多数低蒸汽压酸可以用于并且适合于特定应用。以下列表的酸作为实例给出:多氟烯烃磺酸、全氟烯烃磺酸、多氟芳基磺酸、全氟芳基磺酸、至多50%的氢或氟原子被氯原子取代的酸、CF3(CF2)nSO3H、HO3S(CF2CH2)nSO3H、CF23(CF2CH2)nSO3H、HO3S(CF2)nSO3H,其中n是具有1~9的值的整数、NafionTM离聚物、HCl、HBr、磷酸、硫酸及其混合物。
作为替代方案,固体电解质膜是质子传导膜(PCM),并且其包括典型直径尺寸基本上小于50nm,优选小于3nm,更优选小于1.5nm的孔隙。
根据本发明的另一种膜是如美国专利6,811,911(其全文通过引用并入本文)中所描述的由质子传导基体制成的膜。离子导电基体包括:(i)5~60体积%的具有良好的水性电解质吸附能力的无机粉末;(ii)5~50体积%的聚合物粘合剂,其与水性电解质化学相容;和(iii)10~90体积%的水性电解质,其中所述无机粉末基本上包含亚微米粒子,尺寸优选为约5~约150nm。本发明的基体可任选地包含约0.1~约25%的非挥发性液体润滑剂,其与基体中的所有组分化学相容。
根据本发明的一个优选实施方案,所述无机粉体的特征在于,具有至少10m2/g的表面积并且具有良好的水性电解质吸附能力。
优选地,本发明的基体的无机粉末是选自SiO2、ZrO2、B2O3、TiO2、Al2O3等中的一种。
本发明的基体中使用的聚合物粘合剂是与所用的水性电解质化学相容的物质,即不溶于电解质的物质,并且是选自以下的一种:聚偏二氟乙烯(PVDF)、聚偏二氟乙烯-六氟丙烯(PVDHFP)、聚四氟乙烯(PTFE)、聚甲基丙烯酸甲酯(PMMA)、聚磺酰胺、聚丙烯酰胺、聚氯乙烯(PVC)、聚丙烯腈、聚氟乙烯及其任意组合。
根据本发明的酸(也可以是酸的混合物)可以是纯酸或溶解在水中或本领域已知的其他合适的非水溶剂中的酸。根据本发明合适的酸是:CF23(CF2)nSO3H、HO3S(CF2)nSO3H,其中n是具有1~9的值的整数、硫酸、HCl、HBr、磷酸、HNO3等。优选的酸为CF3(CF2)nSO3H或HO3S3S(CF2)nSO3H,其中n等于0、1、2、3或4。这些优选的酸可以其纯形式使用或作为摩尔浓度为10%~99%,优选摩尔浓度为25%~99%的水溶液使用。
本发明的PCM包括具有良好机械性能的塑料膜的一般外观。它通常可以弯曲约180°而基本不发生实质性的断裂,并且它可以制备成约10~约1000微米或以上的厚度。由于它的稳定性和良好的离子导电性,它可以在从零度以下到约150℃的大温度范围内使用。
根据本发明的一个优选实施方案,当基体制备成膜时,包含在基体中的无机粉末是非常微细、粒径优选小于150nm的非导电粉末。根据该实施方案,其中吸附有水性电解质的PCM孔非常小,并且其特征尺寸基本上小于50nm。
膜对所使用的酸或水性电解质的吸附能力或保留能力取决于几个参数,其中包括无机粉末的组成和类型、聚合物粘合剂、和溶解的酸或电解质的类型。应该优化这些参数的组合以调节各个应用的产品。虽然进行这样的优化,但是应考虑无机粉末含量越高则机械性能越差这一事实。增加基体的无机粉末含量会增加其电解质保留特性,但同时会降低其机械强度。另一方面,增加基体中聚合物粘合剂的含量会增加基体的强度,但会降低基体的润湿性,从而导致其传导性下降。
根据本发明的又一个实施方案,基体的润湿性的改善以及随之而来的电解质保留特性的改善是通过在膜中添加多价金属盐例如Al、Zr、B、Ti等的盐来实现的。
基体的润湿性的改善以及随之而来的电解质保留特性的改善是通过在膜制备前利用酸或碱对无机粉末进行预处理来实现的。
实施例1(28-12版本,60%的孔隙体积):
将200克的PVDF和105.6克的表面积为400平方米/克的二氧化硅(硅石)混合。在不同的烧瓶中,混合加工溶剂(241.6克DBP和1320克DMF)和流变控制剂(10克SPAN80和0.6克Zonil)。将粉末在室温下以低混合速率(200rpm)在溶剂中分散3小时。将混合速率提高到500rpm,同时在40℃下加热16小时。再在室温下以300rpm搅拌16小时进行脱气(移除包埋在混合物中的空气),接着在35℃下的受控温度环境下放置6小时,但不搅拌。然后,将溶液转移到涂布机(Dixon Model 160MK2,如http://www.dixontechnologies.com/marketspilot.htmn中所描述)上,其装载有NIR-LNR-0063R-01型硅化纸。刀间隙设置为180微米,滚动速度设置为0.5米/分钟。
所得干膜具有40~60微米,优选50~55微米的厚度,并且包含有液体物质DBP,其用作成孔剂(为高粘度的油性物质),以及一些其他的残余溶剂。在5~20kg/cm2的压力、140~145℃下将2-6个膜层合在一起3~10分钟以提供具有更好的机械性能的膜。在层合之后进行提取过程,以将成孔剂从空隙中“排出”,产生具有小孔隙的多孔膜,其中孔隙尺寸小于30nm,优选小于3nm,更特别是小于1.5nm。所述提取阶段包括以下几个步骤:
-乙醚∶乙醇浴,包含1∶9比例的这些溶剂,所述膜浸没在该浴中2小时以提取孔隙中的DBP;
-乙醇浴,用以移除残留的DBP和其他潜在溶剂,持续2小时;和
-水浴(去离子水)-用以移除孔隙中的乙醇。
实施例2(32-8版本,60%的孔隙体积):
混合和浇铸过程与实施例1中所述的相同,只是材料量按下式进行了修改:284.8克的PVDF、88克的硅石、311.8克DBP、12.5克SPAN80、1377.4克DMF、0.2克Zonil。
实施例3:
对实施例1和2的膜在用3M硫酸煮沸1小时后,利用Solareon 1260进行室温电导率测试。实施例1和2电导率分别为0.144S/cm-1和0.102S/cm-1。电导率增加是因为它具有良好的酸吸附。下表1示出利用过去的手工小规模方法制造的以及现在所用的更新的自动方法所制造的几种膜的电导率。总体而言,放大的工艺过程使膜的电导率性质保持在0.1~0.2S/cm-1的可接受范围内。
表1:各种手工制造和机器制造的NP-PCM的电导率
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iV-Electrochemical and Solid Letters,7(12)(2004)507
V-Electrochemical and Solid Letters,6(12)A268-A271(2003)
实施例4:
下表2汇总了本发明的质子传导膜的制造方法与常规方法步骤的差异
大部分的改进导致节省时间和劳动,即更高质量的产出膜的更高效方法。该方法的再现性是可靠和简单的:膜是均质的并且具有更高强度,对膜的物理性质只有微小的、可忽略的影响-在可接受的范围和统计误差之内,如表1中所示。
Claims (26)
1.一种用于生产质子传导膜的方法,所述方法包括:
混合(i)5体积%~60体积%的具有良好的酸吸附能力的非导电无机粉末,所述粉末包括基本纳米尺寸的粒子;(ii)5体积%~50体积%的聚合物粘合剂,其与酸、氧化剂和燃料是化学相容的;和(iii)10体积%~90体积%的酸或酸的水溶液,其中所述混合在不同的速率步骤下进行,由此生产一种混合物;
将所述混合物在环境温度下连续浇铸在卷绕的纸或非织造基质上;
将所述经浇铸的混合物在大于100℃的温度下干燥,由此形成干膜;和
将多个所述干膜在压力下层合在一起,并随后从所述干膜的孔隙中提取成孔剂,由此形成平均孔径小于30纳米的所述质子传导膜。
2.根据权利要求1所述的方法,其中将至少4个所述干膜层合到一起。
3.根据权利要求1所述的方法,其中所述混合步骤的所述不同的速率步骤包括:
室温下在约100~500rpm的混合速率下混合1~5小时;
约30~50℃下在约400~700rpm的混合速率下混合10~20小时;
室温下在约100~400rpm的混合速率下混合10~20小时;和
在约30~50℃的温度范围下脱气5~30小时。
4.根据权利要求1所述的方法,其中所述干膜的厚度为约40~60微米。
5.根据权利要求4所述的方法,其中所述干膜的厚度为约50~55微米。
6.根据权利要求1所述的方法,其中所述干膜的所述层合步骤在约5~20kg/cm2的压力和约140~145℃的温度下进行约3~10分钟。
7.根据权利要求1所述的方法,其中所述质子传导膜的平均孔径小于3nm。
8.根据权利要求7所述的方法,其中所述质子传导膜的平均孔径小于1.5nm。
9.根据权利要求1所述的方法,其中所述干燥步骤进行约5~60分钟。
10.根据权利要求1所述的方法,其中所述质子传导膜基本没有裂纹。
11.根据权利要求1所述的方法,还包括在混合前添加至少一种流变控制剂。
12.根据权利要求1所述的方法,其中所述提取步骤包括:
(a)将含有成孔剂的所述质子传导膜在乙醚/乙醇混合物中浸渍足以从所述质子传导膜的孔隙中移除所述成孔剂的时间段;
(b)将来自步骤(a)的所述质子传导膜在乙醇中浸渍以移除任何残留的成孔剂和其他溶剂;以及
(c)将所述质子传导膜在水中浸渍以从所述孔隙中移除乙醇。
13.根据权利要求12所述的方法,其中所述乙醚/乙醇混合物具有约1∶9~3∶7的比例。
14.根据权利要求12所述的方法,其中所述浸渍步骤(a)进行约1~5小时。
15.根据权利要求12所述的方法,其中所述浸渍步骤(b)进行约1~5小时。
16.根据权利要求1所述的方法,其中所述无机粉末为选自SiO2、ZrO2、B2O3、TiO2、Al2O3以及Ti、Al、B和Zr的氢氧化物和氧氢氧化物中的至少一种粉末。
17.根据权利要求1所述的方法,其中所述聚合物粘合剂是选自以下的至少一种粘合剂:聚偏二氟乙烯、聚偏二氟乙烯-六氟丙烯、聚四氟乙烯、聚甲基丙烯酸甲酯、聚磺酰胺、聚丙烯酰胺、聚氯乙烯、丙烯腈、聚氟乙烯和三氟氯乙烯均聚物。
18.根据权利要求1所述的方法,其中所述酸是选自以下的至少一种:多氟烯烃磺酸、全氟烯烃磺酸、多氟芳基磺酸、全氟芳基磺酸、其中至多50%的氢或氟原子被氯原子取代的上述酸、CF3(CF2)nSO3H、HO3S(CF2CH2)nSO3H、CF23(CF2CH2)nSO3H、HO3S(CF2)nSO3H,其中n是具有1~9的值的整数、全氟磺酸共聚物、HCl、HBr、磷酸和硫酸。
19.根据权利要求18所述的方法,其中所述多氟芳基磺酸是选自多氟苯磺酸、多氟甲苯磺酸和多氟苯乙烯磺酸中的至少一种。
20.根据权利要求18所述的方法,其中所述全氟芳基磺酸是选自全氟苯磺酸、全氟甲苯磺酸和全氟苯乙烯磺酸中的至少一种。
21.根据权利要求1所述的方法,还包括至少一种成孔剂,所述成孔剂选自:邻苯二甲酸二丁酯、邻苯二甲酸二乙酯、邻苯二甲酸二甲酯、碳酸亚丙酯和碳酸亚乙酯。
22.根据权利要求11所述的方法,其中所述流变控制剂是选自山梨醇单油酸酯C24H44O6和非离子含氟表面活性剂(C2H4O)x(CF2)yC2H5FO中的至少一种。
23.根据权利要求1所述的方法,还包括再捕获所述酸或酸的水溶液的步骤。
24.根据权利要求1所述的方法,其中所述连续浇铸所述质子传导混合物的步骤使用在卷绕的纸、非织造基体或类似的辊对辊载体支持物上进行溶液涂布的涂布机进行。
25.根据权利要求24所述的方法,其中所述载体支持物是硅化纸,并且所述载体支持物的滚动速度根据所述质子传导混合物的比重来设置。
26.一种通过根据权利要求1所述的方法形成的质子传导膜。
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