CN116742082A - 一种磁性纳米颗粒负载磷钨酸-磺化聚醚醚酮复合质子交换膜的制备方法 - Google Patents
一种磁性纳米颗粒负载磷钨酸-磺化聚醚醚酮复合质子交换膜的制备方法 Download PDFInfo
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Abstract
本发明公开了一种磁性纳米颗粒负载磷钨酸‑磺化聚醚醚酮复合质子交换膜的制备方法。该膜是由负载有磷钨酸的磁性纳米颗粒与磺化聚醚醚酮共混液在磁场下成膜;其制备方法包括:由聚醚醚酮制备磺化聚醚醚酮;用三氯化铁和硫酸亚铁共沉淀合成磁性纳米颗粒;用聚多巴胺包覆磁性纳米颗粒,在颗粒表面引入胺基;将聚多巴胺包覆的磁性纳米颗粒浸泡于磷钨酸溶液中得到负载磷钨酸的磁性纳米颗粒;将负载磷钨酸的磁性纳米颗粒与磺化聚醚醚酮共混,在施加磁场的条件下加热成膜,得到磁性纳米颗粒有序排布的复合质子交换膜。本发明原料易得,操作简单,较易构建出垂直膜面方向质子传输通道,制备的复合质子交换膜用于燃料电池,具有较好的质子传导性能。
Description
技术领域
本发明涉及一种磁性纳米颗粒负载磷钨酸-磺化聚醚醚酮复合质子交换膜的制备方法,属于质子交换膜燃料电池领域。
背景技术
质子交换膜燃料电池作为一种电化学装置,将氢和氧转化为水并在此过程中产生电能,具有高效、环保的优点。质子交换膜作为燃料电池膜电极的核心部件之一,要求具有高质子传导率、良好的热和化学稳定性、较低的气体透过率。常见的质子交换膜材料主要包括全氟磺酸膜(如 )、磺化芳香烃聚合物膜(如磺化聚醚醚酮、磺化聚芳醚砜、磺化聚酰亚胺)等。目前采用的全氟磺酸膜成本较高,且须加工为超薄膜以降低质子传输阻力,会导致膜的机械强度下降,燃料透过率升高。磷钨酸(化学式为H3PW12O40)作为杂多酸中的强酸,其哈米特酸度函数H0=-13.16,达到超强酸的标准,即使在低pH值下,磷钨酸的三个质子也是完全解离。将磷钨酸掺入到聚合物膜材料中制备复合质子交换膜,可以为质子交换膜提供额外的质子传输位点,提高质子传导率。同时,磷钨酸具有强吸水性能,在低湿度下可使复合质子交换膜保持一定的质子传导率。但是,磷钨酸易溶于水,质子交换膜工作在水环境条件下磷钨酸容易流失,导致膜的质子传导性能下降。为防止磷钨酸流失,研究人员进行了诸多有益的尝试。比如将磷钨酸填充在碳纳米管内,再与Nafion共混制备复合质子交换膜,碳纳米管既起到物理固载磷钨酸的作用,又构成长程的离子传输通道(Nano Energy 2016,23,114–121)。又如通过酸碱对作用,将磷钨酸负载于表面富含有胺基的纳米管或纳米片上,再将其与磺化聚合物共混制膜,有效提高了膜的质子传导率(Polymer Testing 2019,73:242–249;International Journal of Hydrogen Energy2020,45(35):17782–17794)。上述所制备的磷钨酸构成的复合质子交换膜,其质子传输通道是随机排布的,即质子传导率在膜的水平方向和垂直方向基本一致。若沿垂直膜面方向构建垂直通道,则可以缩短质子传输路径,有利于燃料电池性能的提高。因此,本研究合成了表面富含胺基的磁性纳米颗粒并负载磷钨酸,将其与磺化聚醚醚酮共混并施加垂直方向磁场制膜,磁性纳米颗粒在磁场作用下有序排布,构成垂直膜面方向质子传输通道,缩短质子传输路径,提高质子传导性能。
发明内容
本发明的目的在于提供一种磁性纳米颗粒负载磷钨酸-磺化聚醚醚酮复合质子交换膜的制备方法。该制备方法过程简单,所制备的复合质子交换膜在垂直膜面方向质子传输阻力小,用于质子交换膜燃料电池具有较好的质子传导性能。
本发明是通过以下技术方案实现的,一种磁性纳米颗粒负载磷钨酸-磺化聚醚醚酮复合质子交换膜,该膜是由负载磷钨酸的磁性纳米颗粒与磺化度为50~60%的磺化聚醚醚酮,按质量比0.05~5:100,在磁场作用下形成厚度为30~60μm的复合质子交换膜,其中四氧化三铁磁性纳米颗粒直径在20~50nm,聚多巴胺包覆层厚度在10~30nm,磷钨酸在磁性纳米颗粒上的负载量10~30wt%,施加磁场的磁感应强度为0.05~0.5T。
上述负载磷钨酸磁性纳米颗粒-磺化聚醚醚酮复合质子交换膜的制备方法,包括以下过程:
(1)磺化聚醚醚酮的制备:
将充分干燥的聚醚醚酮粉末加入到质量分数为98%的浓硫酸中,聚醚醚酮与浓硫酸质量比为5~15:100,室温下搅拌使其完全溶解,再升温至50~60℃进行磺化反应1~3h,冷却后倒入冰水中沉淀析出,用去离子水多次洗涤至中性,60℃真空干燥24h,得到磺化度50~60%的磺化聚醚醚酮。
(2)负载磷钨酸的磁性纳米颗粒的制备:
a.制备Fe3O4纳米颗粒。采用共沉淀法制备Fe3O4纳米颗粒,将FeCl3与FeSO4按摩尔比2:1溶解到除氧的去离子水中得到铁盐溶液,总铁盐与水的质量比为5~10:100,机械搅拌并在氮气气氛下加热至80℃。将浓氨水快速加入到铁盐溶液中并反应5分钟,浓氨水与铁盐溶液体积比为10~20:100,然后加入1mol/L柠檬酸钠溶液以防止颗粒团聚,柠檬酸钠溶液与铁盐溶液体积比为2~5:100。连续搅拌2~5h后,用永磁铁收集沉淀物,并用去离子水多次洗涤至中性,最后将黑色沉淀用乙醇洗涤两次,并在60℃真空干燥,得到Fe3O4磁性纳米颗粒。
b.聚多巴胺包覆磁性纳米颗粒。将Fe3O4磁性纳米颗粒超声分散于水中,得到质量分数为1~3%分散液,再取分散液10mL加入到90mL的10mmol/L的Tris缓冲溶液中,用0.1mol/L的稀盐酸调节pH值至8.5,超声使纳米颗粒分散均匀。加入盐酸多巴胺0.1~0.3g,30℃在空气气氛下剧烈搅拌反应6h,使聚多巴胺充分包覆于磁性纳米颗粒表面。用去离子水、乙醇交替洗涤多次,在60℃真空干燥,得到聚多巴胺包覆磁性纳米颗粒。
c.负载磷钨酸。将聚多巴胺包覆磁性纳米颗粒分散到质量浓度为5~10%的磷钨酸N,N-二甲基甲酰胺溶液中,待磷钨酸与磁性纳米颗粒表面胺基充分反应后,用强磁铁分离出磁性纳米颗粒,并用N,N-二甲基甲酰胺洗涤去除多余的磷钨酸,最后用乙醇洗涤2次,60℃真空干燥得到负载磷钨酸的磁性纳米颗粒。
(3)复合质子交换膜的制备:
将步骤(1)制备的磺化聚醚醚酮溶解于N-甲基吡咯烷酮中,制得质量分数为8~10%磺化聚醚醚酮溶液。将步骤(2)制备的负载磷钨酸的磁性纳米颗粒超声分散在N-甲基吡咯烷酮中,制得质量分数为0.5~2%的分散液。将负载磷钨酸磁性纳米颗粒分散液与磺化聚醚醚酮溶液混合,磁性纳米颗粒与磺化聚醚醚酮的质量比为0.05~5:100,机械搅拌并超声分散使其混合均匀,静置2h脱泡得到铸膜液。将铸膜液倒入培养皿中,置于垂直液面方向的磁场下,于60℃干燥成膜,磁场使用磁场发生器控制,磁感应强度控制在0.05~0.5T。将所制备的膜在2mol/L的盐酸溶液中酸化处理24h,再水洗至中性,干燥后得到厚度为30~60μm的磁性纳米颗粒负载磷钨酸-磺化聚醚醚酮复合质子交换膜。
本发明制得的磁性纳米颗粒负载磷钨酸-磺化聚醚醚酮复合质子交换膜能用作燃料电池质子交换膜。
本发明的优点在于:所用原料易得,操作简单,磁感应强度大小可控且容易实现。将负载了磷钨酸的磁性纳米颗粒与磺化聚醚醚酮在磁场下成膜,构建出了垂直膜面方向质子传输通道,缩短质子传输路径,制备的复合质子交换膜用于燃料电池,具有较好的质子传导性能。
附图说明
图1为实施例1在施加磁场的条件下制备的磁性纳米颗粒负载磷钨酸-磺化聚醚醚酮复合质子交换膜的断面场发射扫描电子显微镜(FESEM)照片。
图2为对比例1在不施加磁场的条件下制备的磁性纳米颗粒负载磷钨酸-磺化聚醚醚酮复合质子交换膜的断面场发射扫描电子显微镜(FESEM)照片。
图3为实施例2制备的纯磺化聚醚醚酮膜的断面场发射扫描电子显微镜(FESEM)照片。
图4所示为实施例1,实施例2所制得的膜1,膜2,以及对比例1,对比例2制得的膜3,膜4的质子传导率测试结果。
具体实施方式
实施例1
将聚醚醚酮粉末于80℃下真空干燥24h,取10g粉末加入到100mL 98%浓硫酸中,在20℃下机械搅拌溶解12h,再升温至50℃反应1.5h,立刻用冷水降温终止反应,将反应溶液缓慢倒入大量冰水中沉析,得到纤维状产物,使用去离子水多次洗涤产物,直至洗涤水接近中性,最后将产物放入60℃真空烘箱中干燥24h,得到磺化度为50%的磺化聚醚醚酮。
在三口烧瓶中加入100mL除氧去离子水,再加入FeCl3·6H2O(5.4g,20mmol)和FeSO4·7H2O(2.8g,10.07mmol),机械搅拌并在氮气气氛下加热至80℃,将16mL浓氨水快速加入到混合溶液中并反应5分钟,然后加入2mL的1mol/L的柠檬酸钠溶液以防止颗粒团聚。连续搅拌2h后,用永磁铁收集沉淀物,并用去离子水多次洗涤至中性,最后将黑色沉淀用乙醇洗涤两次,并在60℃真空干燥得到Fe3O4磁性纳米颗粒。取0.2g Fe3O4磁性纳米颗粒超声分散于10mL去离子水中,再加入到90mL的10mmol/L的Tris缓冲溶液中,用0.1mol/L的稀盐酸调节pH值至8.5,超声使Fe3O4磁性纳米颗粒分散均匀。加入盐酸多巴胺0.2g,30℃在空气气氛下剧烈搅拌反应6h,用磁铁分离产物,去离子水、乙醇交替洗涤多次,在60℃真空干燥得到聚多巴胺包覆的磁性纳米颗粒。取0.05g聚多巴胺包覆的磁性纳米颗粒分散到10mL含磷钨酸5%的N,N-二甲基甲酰胺溶液中,搅拌12h使磷钨酸与磁性纳米颗粒表面胺基充分反应后,用强磁铁分离出磁性纳米颗粒,并用N,N-二甲基甲酰胺洗涤去除多余的磷钨酸,最后用乙醇洗涤2次,60℃真空干燥得到负载磷钨酸的磁性纳米颗粒,磷钨酸负载量为20wt%。
取0.05g负载磷钨酸的磁性纳米颗粒分散到N-甲基吡咯烷酮中,得到质量分数为1%的分散液。取0.3g磺化度为50%的磺化聚醚醚酮溶解于2.5g N-甲基吡咯烷酮中,得到磺化聚醚醚酮溶液,另取分散液0.6g(含固体0.006g)与磺化聚醚醚酮溶液混合,机械搅拌并超声分散使其混合均匀,静置2h脱泡得到铸膜液。将铸膜液倒入直径为8cm的培养皿中,置于磁感应强度为0.3T的垂直磁场中,于60℃干燥24h成膜。将所制备的膜在2mol/L的盐酸溶液中酸化处理24h,再水洗至中性,干燥后得到厚度约为52μm磁性纳米颗粒负载磷钨酸-磺化聚醚醚酮的复合质子交换膜(膜1.M-SP/PWA-MNPs-2)。
实施例2
将聚醚醚酮粉末于80℃下真空干燥24h,取15g粉末加入到100mL 98%浓硫酸中,在20℃下机械搅拌溶解12h,再升温至50℃反应2h,立刻用冷水降温终止反应,将反应溶液缓慢倒入大量冰水中沉析,得到纤维状产物,使用去离子水多次洗涤产物,直至洗涤水接近中性,最后将产物放入60℃真空烘箱中干燥24h,得到磺化度为55%的磺化聚醚醚酮。
在三口烧瓶中加入100mL除氧去离子水,再加入FeCl3·6H2O(5.4g,20mmol)和FeSO4·7H2O(2.8g,10.07mmol),机械搅拌并在氮气气氛下加热至80℃,将16mL浓氨水快速加入到混合溶液中并反应5分钟,然后加入2mL的1mol/L的柠檬酸钠溶液以防止颗粒团聚。连续搅拌2h后,用永磁铁收集沉淀物,并用去离子水多次洗涤至中性,最后将黑色沉淀用乙醇洗涤两次,并在60℃真空干燥得到Fe3O4磁性纳米颗粒。取0.3g Fe3O4磁性纳米颗粒超声分散于100mL去离子水中,再取分散液10mL加入到90mL的10mmol/L的Tris缓冲溶液中,用0.1mol/L的稀盐酸调节pH值至8.5,超声使Fe3O4磁性纳米颗粒分散均匀。加入盐酸多巴胺0.3g,30℃在空气气氛下剧烈搅拌反应6h,用磁铁分离产物,去离子水、乙醇交替洗涤产物多次,在60℃真空干燥得到聚多巴胺包覆的磁性纳米颗粒。取0.1g聚多巴胺包覆的磁性纳米颗粒分散到15mL含磷钨酸5%的N,N-二甲基甲酰胺溶液中,搅拌10h,使磷钨酸与磁性纳米颗粒表面胺基充分反应后,用强磁铁分离出磁性纳米颗粒,并用N,N-二甲基甲酰胺洗涤去除多余的磷钨酸,最后用乙醇洗涤2次,60℃真空干燥,得到负载磷钨酸的磁性纳米颗粒,磷钨酸负载量为18wt%。
取0.1g负载磷钨酸的磁性纳米颗粒分散到N-甲基吡咯烷酮中得到质量分数为1%的分散液。取0.3g磺化度为55%的磺化聚醚醚酮溶解于2.5g N-甲基吡咯烷酮中,得到磺化聚醚醚酮溶液,另取分散液1.2g(含固体0.012g)与磺化聚醚醚酮溶液混合,机械搅拌并超声分散使其混合均匀,静置2h脱泡得到铸膜液。将铸膜液倒入直径为8cm的培养皿中,置于磁感应强度为0.2T的垂直磁场中于60℃干燥24h成膜。将所制备的膜在2mol/L的盐酸溶液中酸化处理24h,再水洗至中性,干燥后得到厚度约为55μm磁性纳米颗粒负载磷钨酸-磺化聚醚醚酮的复合质子交换膜(膜2.M-SP/PWA-MNPs-4)。
对比例1
将聚醚醚酮粉末于80℃下真空干燥24h,取10g粉末加入到100mL 98%浓硫酸中,在20℃下机械搅拌溶解12h,再升温至50℃反应1.5h,立刻用冷水降温终止反应,将反应溶液缓慢倒入大量冰水中沉析,得到纤维状产物,使用去离子水多次洗涤产物,直至洗涤水接近中性,最后将产物放入60℃真空烘箱中干燥24h,得到磺化度为50%的磺化聚醚醚酮。
在三口烧瓶中加入100mL除氧去离子水,再加入FeCl3·6H2O(5.4g,20mmol)和FeSO4·7H2O(2.8g,10.07mmol),机械搅拌并在氮气气氛下加热至80℃,将16mL浓氨水快速加入到混合溶液中并反应5分钟,然后加入2mL的1mol/L的柠檬酸钠溶液以防止颗粒团聚。连续搅拌2h后,用永磁铁收集沉淀物,并用去离子水多次洗涤至中性,最后将黑色沉淀用乙醇洗涤两次,并在60℃真空干燥得到Fe3O4磁性纳米颗粒。取0.2g Fe3O4磁性纳米颗粒超声分散于100mL去离子水中,再取分散液10mL加入到90mL的10mmol/L的Tris缓冲溶液中,用0.1mol/L的稀盐酸调节pH值至8.5,超声使Fe3O4磁性纳米颗粒分散均匀。加入盐酸多巴胺0.2g,30℃在空气气氛下剧烈搅拌反应6h,用磁铁分离产物,用去离子水、乙醇交替洗涤产物多次,然后在60℃真空干燥,得到聚多巴胺包覆的磁性纳米颗粒。取0.05g聚多巴胺包覆的磁性纳米颗粒分散到10ml含磷钨酸5%的N,N-二甲基甲酰胺溶液中,搅拌12h使磷钨酸与磁性纳米颗粒表面胺基充分反应后,用强磁铁分离出磁性纳米颗粒,并用N,N-二甲基甲酰胺洗涤去除多余的磷钨酸,最后用乙醇洗涤2次,60℃真空干燥得到负载磷钨酸的磁性纳米颗粒,磷钨酸负载量为20wt%。
取0.05g负载磷钨酸的磁性纳米颗粒分散到N-甲基吡咯烷酮中得到质量分数为1%的分散液。取0.3g磺化度为50%的磺化聚醚醚酮溶解于2.5g N-甲基吡咯烷酮中,得到磺化聚醚醚酮溶液,另取分散液0.6g(含固体0.006g)与磺化聚醚醚酮溶液混合,机械搅拌并超声分散使其混合均匀,静置2h脱泡得到铸膜液。将铸膜液倒入直径为8cm的培养皿中,不施加磁场,直接于60℃干燥24h成膜。将所制备的膜在2mol/L的盐酸溶液中酸化处理24h,再水洗至中性,干燥后得到厚度约为54μm磁性纳米颗粒负载磷钨酸-磺化聚醚醚酮复合质子交换膜(膜3.SP/PWA-MNPs-2)。
对比例2
将聚醚醚酮粉末于80℃下真空干燥24h,取10g粉末加入到100mL 98%浓硫酸中,在20℃下机械搅拌溶解12h,再升温至50℃反应1.5h,立刻用冷水降温终止反应,将反应溶液缓慢倒入大量冰水中沉析,得到纤维状产物,使用去离子水多次洗涤产物,直至洗涤水接近中性,最后将产物放入60℃真空烘箱中干燥24h,得到磺化度为50%的磺化聚醚醚酮。
取0.3g磺化度为50%的磺化聚醚醚酮溶解于3g N-甲基吡咯烷酮中,静置2h脱泡得到铸膜液。将铸膜液倒入直径为8cm的培养皿中,置于磁感应强度为0.3T的垂直磁场中于60℃干燥24h成膜。将所制备的膜在2mol/L的盐酸溶液中酸化处理24h,再水洗至中性,干燥后得到厚度约为55μm的纯磺化聚醚醚酮膜(膜4.SPEEK)。
本发明未尽事宜为公知技术。
上述实施例只为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。
Claims (1)
1.一种磁性纳米颗粒负载磷钨酸-磺化聚醚醚酮复合质子交换膜的制备方法,其特征在于,该膜是由负载磷钨酸的磁性纳米颗粒与磺化度为50~60%的磺化聚醚醚酮按质量比0.05~5:100在磁场下形成的厚度为30~60μm的复合质子交换膜,其中四氧化三铁磁性纳米颗粒直径为20~50nm,聚多巴胺包覆层厚度为10~30nm,磷钨酸在磁性纳米颗粒上的负载量为10~30wt%,施加磁场的磁感应强度为0.05~0.5T;
该膜制备方法包括以下过程:
磺化聚醚醚酮的制备:
将充分干燥的聚醚醚酮粉末加入到质量分数为98%的浓硫酸中,聚醚醚酮与浓硫酸质量比为5~15:100,室温下搅拌使其完全溶解,再升温至50~60℃进行磺化反应1~3h,冷却后倒入冰水中沉淀析出,用去离子水多次洗涤至中性,60℃真空干燥24h,得到磺化度50~60%的磺化聚醚醚酮;
负载磷钨酸的磁性纳米颗粒的制备:
(1)将FeCl3与FeSO4按摩尔比2:1溶解到除氧的去离子水中得到铁盐溶液,总铁盐与水的质量比为5~10:100,机械搅拌并在氮气气氛下加热至80℃;将浓氨水快速加入到铁盐溶液中并反应5分钟,浓氨水与铁盐溶液体积比为10~20:100,加入1mol/L柠檬酸钠溶液以防止颗粒团聚,柠檬酸钠溶液与铁盐溶液体积比为2~5:100;连续搅拌2~5h后,用永磁铁收集沉淀物,得到Fe3O4磁性纳米颗粒;
(2)将步骤(1)制备的Fe3O4磁性纳米颗粒超声分散于水中,得到质量分数为1~3%的分散液,再取分散液10mL加入到90mL pH值为8.5的Tris缓冲溶液中,加入盐酸多巴胺0.1~0.3g,30℃在空气气氛下剧烈搅拌反应6h,使聚多巴胺充分包覆于磁性纳米颗粒表面,得到聚多巴胺包覆的磁性纳米颗粒;
(3)将步骤(2)制备的聚多巴胺包覆的磁性纳米颗粒分散到含磷钨酸5~10wt%的N,N-二甲基甲酰胺溶液中,待磷钨酸与磁性纳米颗粒表面胺基充分反应后,用强磁铁分离出磁性纳米颗粒,并用N,N-二甲基甲酰胺洗涤去除多余的磷钨酸,用乙醇洗涤2次,干燥得到负载磷钨酸的磁性纳米颗粒;
复合质子交换膜的制备:
将制备的磺化聚醚醚酮溶解于N-甲基吡咯烷酮中,制得质量分数为8~10%的磺化聚醚醚酮溶液;将负载磷钨酸的磁性纳米颗粒超声分散在N-甲基吡咯烷酮中,制得质量分数为0.5~2%的分散液;将分散液与磺化聚醚醚酮溶液混合,磁性纳米颗粒与磺化聚醚醚酮的质量比为0.05~5:100,机械搅拌并超声分散使其混合均匀,静置2h脱泡得到铸膜液;将铸膜液倒入培养皿中,置于垂直方向的磁场下于60℃干燥成膜,磁场使用磁场发生器控制,磁感应强度控制在0.05~0.5T;将所制备的膜在2mol/L的盐酸溶液中酸化处理24h,再水洗至中性,干燥后得到厚度为30~60μm的磁性纳米颗粒负载磷钨酸-磺化聚醚醚酮复合质子交换膜,用于燃料电池。
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CN117199466B (zh) * | 2023-11-07 | 2024-03-12 | 杭州德海艾科能源科技有限公司 | 一种钒液流电池用高电导率复合膜及其制备方法 |
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