CN114855205A - 一种多级结构的三元金属硫化物三维电极的制备方法 - Google Patents
一种多级结构的三元金属硫化物三维电极的制备方法 Download PDFInfo
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Abstract
本发明提供了一种多级结构的三元金属硫化物三维电极的制备方法,包括:将泡沫镍置于六水硝酸镍,六水硝酸钴,氟化铵和尿素的混合水溶液中水热合成镍钴前驱物,再将覆盖了镍钴前驱物的泡沫镍浸入50mM FeCl3溶液中10min,随后取出泡沫镍并置于80℃烘箱中干燥1h,得到FeOOH修饰镍钴前驱物的泡沫镍三维电极;将P2S5和该前驱物放置在管式炉上、下游的两个单独瓷舟中,在惰性气氛中进行煅烧,经过洗涤处理得到具有多级结构的三元金属硫化物三维电极。本发明利用浸渍法和低温硫化煅烧法生成具有多级结构的三元金属硫化物并实现其在泡沫镍电极表面的均匀覆盖。
Description
技术领域
本发明属于氢能源燃料电池技术领域,具体涉及一种多级结构的三元金属硫化物三维电极的制备方法。
背景技术
过度使用传统化石燃料导致了严重的环境污染和能源危机,迫使我们开发环境友好、可回收的替代能源如太阳能、风、潮汐、地热能、氢能。氢气作为一种高效、清洁的能源载体,被认为是最有前途的化石燃料替代品之一。电催化水分解是一种很有应用前景的氢能生产方法,它由阴极的析氢反应(HER)和阳极的析氧反应(OER)组成。然而,电催化水分解技术需要克服很高的过电位才能获取足够的氢能,极大限制了其能量转化效率。因此,设计高催化活性的电催化剂是提高电催化水分解性能的重要途经。近年来,贵金属催化剂,如铂或铱等材料,被认为是最高效的HER/OER电催化剂体系。然而,由于其成本高和稀缺性等缺点,导致贵金属材料在电催化水分解领域的实际应用受到严重限制。基于此,发展高效稳定的非贵金属材料并用作电催化水分解的双功能电催化剂具有重要研究意义。
目前,过渡金属硫化物具有独特的3d电子结构和高导电性的协同优势,被广泛制备并用作HER/OER电催化剂。然而,由于缺乏更多可调参数,单组分硫化物的催化活性极为有限。在这方面,人们致力于通过设计更多的界面异质结构或引入更多的金属催化中心来提高过渡金属硫化物的催化性能。丰富的杂界面和多金属催化中心可以提供更多的催化活性位点,调节电子结构和表面性质,从而显著改善电催化性能。此外,直接生长催化剂的三维电极构型也具有更大的比表面积、更快速的气液传质及更快速的电荷转移速率,因此是用于设计高性能电极材料的理想模型。通过将多金属催化中心的电催化剂与三维支撑电极相结合,是实现催化性能协同增强的有效策略。然而,传统硫化物的合成温度较高,造成材料表面结构的严重团聚,这不利于暴露更多催化位点及界面的电子转移。因此,发展低温合成策略对于制备多元金属硫化物三维电极至关重要。
发明内容
针对现有技术中的问题,本发明提供一种多级结构的三元金属硫化物三维电极的制备方法,利用浸渍法和低温硫化煅烧法生成具有多级结构的三元金属硫化物并实现其在泡沫镍电极表面的均匀覆盖。
为实现以上技术目的,本发明的技术方案是:
一种多级结构的三元金属硫化物三维电极的制备方法,包括如下步骤:
将六水硝酸镍,六水硝酸钴,氟化铵和尿素加入水中形成混合水溶液,然后将泡沫镍置于混合水溶液中进行水热合成镍钴前驱物,最后将制备好的镍钴前驱物进浸入50mMFeCl3溶液中10min,随后取出再放入80℃烘箱中干燥1h,得到FeOOH修饰的镍钴前驱物;其中,形成FeOOH的反应过程为含有Fe3+离子的水溶液在镍钴前驱物表面发生水解,并进一步在80℃下缓慢烘干。
将FeOOH修饰的镍钴前驱物和P2S5依次放置在管式炉的下游和上游的两个单独的瓷舟中,在惰性气氛中进行煅烧,经过洗涤处理得到具有多级结构的三元金属硫化物三维电极。
进一步,所述混合水溶液中,六水硝酸钴的浓度为25-28mg/mL,六水硝酸镍的浓度为25-28mg/mL,氟化铵的浓度为1.5-1.8mg/mL,尿素的浓度为55-65mg/mL。
进一步的,所述泡沫镍在使用前进行预处理,所述预处理是将泡沫镍依次经丙酮、乙醇、去离子水交替清洗3次,然后在酸性溶液中浸泡,再用去离子水和乙醇充分清洗,干燥并储存于惰性气氛中。其中,酸溶液采用稀盐酸或者稀硫酸,且所述酸溶液的浓度为0.05-0.1mol/L。
进一步的,所述水热合成是将泡沫镍置于六水硝酸镍,六水硝酸钴,氟化铵和尿素的混合水溶液加热处理,所述水热反应的温度为120℃,反应时间为6-8h,反应溶液体积占水热釜容积的70%。
进一步的,所述FeOOH修饰的镍钴前驱物与P2S5不直接接触,其两者的距离为2-3cm,所述FeOOH修饰的镍钴前驱物与P2S5的质量比为3-6:1,所述瓷舟为石英、Al2O3、Si3N4或BN材质的高温瓷舟。
所述管式炉必须具有良好的密封性,以确保在高温煅烧过程中P2S5充分充斥瓷舟反应腔体与FeOOH修饰的镍钴前驱物反应。所述煅烧的具体步骤包括:将瓷舟置于耐高温的石英管中,充入惰性气体,待通入惰性气体5-10min后完全充满石英管及瓷舟,将石英管放入高温管式炉中进行煅烧,且所述煅烧以10℃/min的升温速率在260-280℃煅烧2h,然后以5℃/min的降温速率降至室温,且所述石英管保持干燥;所述惰性气体采用氮气、氦气和氩气中的任意一种或多种,且所述惰性气体的纯度为99.99%,且所述惰性气体的流速为1-3sccm/s。
煅烧得到的覆盖有FeCoNiSx样品的所述泡沫镍三维电极(FeCoNiSx/NF;NF为泡沫镍简写)取出并进行洗涤;所述洗涤是将上述样品在蒸馏水、乙醇溶液中交替清洗3次,然后干燥,所述洗涤的具体处理方式为:将样品放入蒸馏水中超声清洗10-30min,再放入乙醇中超声清洗10-30min,之后取出放入50-80℃真空干燥箱中干燥30min,得到所述具有多级结构的三元金属硫化物三维电极。
一种利用上述方法制备的多级结构的三元金属硫化物三维电极,即FeCoNiSx/NF双功能电极材料。
本发明通过水热法将钴镍沉积在泡沫镍表面,形成镍钴前驱体,并采用浸渍法配合静置烘干形成FeOOH修饰的镍钴前驱物;然后采用低温硫化煅烧法,即FeOOH在较低温度下分解释放H2O分子与P2S5反应生成磷酸和硫化氢气体,而硫化氢气体随着惰性气体浸入放置前驱体的瓷舟中作为硫源反应,生成具有多级结构的三元金属硫化物。
从以上描述可以看出,本发明具备以下优点:
1.本发明利用浸渍法和低温硫化煅烧法生成具有多级结构的三元金属硫化物并实现其在泡沫镍电极表面的均匀覆盖。
2.本发明制备的三维电极具有丰富的催化活性中心、强的电子相互作用和高的界面电荷转移能力,具有优异的双功能催化性能。
3.本发明采用的低温法可以在维持高活性位点暴露的前提下,采用更低的合成温度制备具有多级结构的三元金属硫化物三维电极,展现了在电催化水分解领域极高的应用前景。
4.本发明提供的制备方法使用设备简易,只需要瓷舟、水热釜、石英支架及较为常见的化工原料即可进行批量生产,同时,产物与原料也能较为方便的进行回收,展现了更好的重复性和经济性。
5.本发明制备的FeCoNiSx/NF负载的泡沫镍三维电极不需要额外添加粘结剂和导电剂就具有较高的导电性和稳定性,可以快速组装成电极并用于水电解制氢,FeCoNiSx/NF三维电极在HER、OER以及全解水方面都表现出较高的催化活性,且在进行多次循环测试和长时间的计时电流测试后催化活性并未降低。
附图说明
图1为本发明合成样品的XRD衍射花样;
图2为本发明合成样品的SEM形貌图;
图3为本发明合成样品的X射线光电子能谱图;
图4为本发明合成样品的透射和高分辨电子显微镜图;
图5为本发明合成样品在1M KOH下测试得到的析氢(HER)和析氧(OER)反应的线性伏安曲线图;
图6为本发明合成样品在1M KOH条件下通过两电极法所测试的全解水性能图;
图7为本发明合成样品在1M KOH条件下通过两电极法所测试全解水的计时电流曲线图;
图8为本发明合成样品在1M KOH条件下所测试的电化学双电层电容拟合曲线。
具体实施方式
结合图1-图8详细说明本发明的具体实施例,但不对本发明的权利要求做任何限定。
实施例1
首先将一块泡沫镍(1×2cm2)在超声波作用下通过丙酮、乙醇、去离子水冲洗50分钟,去除表面的油污与吸附的杂质,然后在0.02mol/L盐酸溶液中浸泡5min,然后用去离子水超声清洗10-30min,然后放入50-80℃真空干燥箱中干燥30min备用。
取(1×2cm2)上述处理后的泡沫镍放入含有0.4g六水硝酸镍,0.4g六水硝酸钴,0.25g氟化铵和0.9g尿素的15ml混合水溶液中于20ml水热釜120℃下保持6小时水热合成前驱体,然后将制备好的前驱物浸入50mM FeCl3溶液中10min,放入80℃烘箱中干燥1h,将100mg P2S5和FeOOH修饰的镍钴前驱物置在石英管上游和下游的两个单独的瓷舟中,二者距离为1cm,放入充满惰性气氛的管式炉中进行260℃煅烧,升温速率为10℃/min,保温2h后缓慢退火取出,降温速率为5℃/min,然后放入水中超声10min,再放入乙醇中浸泡超声10min,重复三次后取出放入真空干燥箱中以80℃干燥30min后取出。
采用XRD对制备的样品进行分析,结果见图1。由图1可知,所合成的样品包含FeS,CoS和NiS物相,与标准卡片PDF#760965,PDF#750605和PDF#120041相吻合。
对制备的样品进行SEM分析,结果见图2,其中图a是FeCoNiSx/NF的低倍扫描电镜图,图b是FeCoNiSx/NF的高分辨率扫描电镜图,由图3可知FeCoNiSx/NF样品均匀分布在泡沫镍基底上,并且其呈多级结构,有利于在反应过程中与电解液充分接触。
对制备的样品进行X射线光电子能谱分析,结果见图3,其中图a是Co2p的XPS图谱,图b是Ni2p的XPS图谱,图c是S2p的XPS图谱,图d是Fe2p的XPS图谱,由图4可知Fe元素和S元素成功掺入样品中,而P元素并未引入。
对制备的样品进行TEM和HRTEM分析,结果见图4,其中图a是FeCoNiSx从泡沫镍基底上超声得到的形貌,图b是FeCoNiSx样品的HRTEM晶格条纹图,由图5可知,样品0.258nm、0.294nm、0.282nm的晶格间距可分别对应于NiS(002)面、CoS(101)面和FeS(002)面。
图5为本发明制备的样品在1M KOH条件下电催化析氢(图a)和电催化析氧(图b)线性伏安扫描图;从图a和图b中可以看出负载在泡沫镍上的FeCoNiSx样品具有优异的催化性能。在图a中,其在10mAcm-2时的HER过电位只需20mV,而图b中,其OER性能在50mAcm-2的过电位只需要260mV左右。
图6为本发明制备的样品在1M KOH条件下通过两电极法测试的全解水的线性伏安扫描图,其主要是将FeCoNiSx/NF样品同时作为阴极和阳极组成全水解电解池,其在碱性条件下展现出优异的全水解性能,在50mA cm-2和100mA cm-2的电流密度下,其电池电压只需要1.67V和1.8V。
图7为本发明制备的样品在1M KOH条件下通过两电极法以1.6V恒电压工作时的全解水的计时电流曲线图,其主要是将FeCoNiSx/NF样品同时作为阴极和阳极组成两电极全水解电解池,在1.6V恒电位条件下展现出优异的稳定性,经过长时间测试,样品的稳定性良好。
图8为本发明制备的样品在1M KOH条件下所测试的电化学双电层电容拟合曲线。从图中我们可以看出FeCoNiSx/NF样品具有很高的电催化活性面积,这种多级结构能为催化反应提供更多的活性位点。
实施例2:
按照实施例1所述的方法对泡沫镍进行预处理。
取(1×2cm2)上述处理后的泡沫镍放入含0.4g六水硝酸镍,0.4g六水硝酸钴,0.25g氟化铵和0.9g尿素的15ml混合水溶液中于20ml水热釜120℃下保持6小时水热合成前驱体,然后将制备好的前驱物浸入50mM FeCl3溶液中30min,放入80℃烘箱中干燥1h,将100mg P2S5和FeOOH修饰的镍钴前驱物放置在管式炉上游和下游的两个单独的瓷舟中,二者距离2cm,放入充满惰性气氛的管式炉中进行260℃煅烧,升温速率为8℃/min,保温2h后缓慢退火取出,降温速率为5℃/min,然后放入水中超声10min,再放入乙醇中浸泡超声10min,重复三次后取出放入真空干燥箱中以80℃干燥30min后取出。
经测试,合成的样品具有和实施例1样品相当的催化性能。
实施例3:
按照实施例1所述的方法对泡沫镍进行预处理。
取(1×2cm2)上述处理后的泡沫镍放入含0.4g六水硝酸镍,0.4g六水硝酸钴,0.25g氟化铵和0.9g尿素的15ml混合水溶液中于20ml水热釜120℃下保持8小时水热合成前驱体,然后将制备好的前驱物浸入50mM FeCl3溶液中15min,放入80℃烘箱中干燥1h,将100mg P2S5和FeOOH修饰的镍钴前驱物放置在管式炉上游和下游的两个单独的瓷舟中,二者距离2cm,放入充满惰性气氛的管式炉中进行260℃煅烧,升温速率为5℃/min,保温1h后缓慢退火取出,降温速率为10℃/min,然后放入水中超声10min,再放入乙醇中浸泡超声10min,重复三次后取出放入真空干燥箱中以80℃干燥30min后取出。
经测试,合成的样品具有和实施例1样品相当的催化性能。
实施例4:
按照实施例1所述的方法对泡沫镍进行预处理。
取(1×2cm2)上述处理后的泡沫镍放入含0.4g六水硝酸镍,0.4g六水硝酸钴,0.25g氟化铵和0.9g尿素的15ml混合水溶液中于20ml水热釜120℃下保持6小时水热合成前驱体,然后将制备好的前驱物浸入50mM FeCl3溶液中60min,放入70℃烘箱中干燥1h,将100mg P2S5和FeOOH修饰的镍钴前驱物放置在管式炉上游和下游的两个单独的瓷舟中,二者距离2cm,放入充满惰性气氛的管式炉中进行260℃煅烧,升温速率为10℃/min,保温2h后缓慢退火取出,降温速率为10℃/min,然后放入水中超声10min,再放入乙醇中浸泡超声10min,重复三次后取出放入真空干燥箱中以60℃干燥30min后取出。
经测试,合成的样品具有和实施例1样品相当的催化性能。
实施例5:
按照实施例1所述的方法对泡沫镍进行预处理。
取(2×4cm2)上述处理后的泡沫镍放入含1.6g六水硝酸镍,1.6g六水硝酸钴,1g氟化铵和3.6g尿素的60ml混合水溶液中于100ml水热釜120℃下保持6小时水热合成前驱体,然后将制备好的前驱物浸入50mM FeCl3溶液中30min,放入80℃烘箱中干燥1h,将400mgP2S5和FeOOH修饰的镍钴前驱物放置在管式炉上游和下游的两个单独的瓷舟中,二者距离2cm,放入充满惰性气氛的管式炉中进行260℃煅烧,升温速率为8℃/min,保温2h后缓慢退火取出,降温速率为5℃/min,然后放入水溶液中超声10min,再放入乙醇溶液中浸泡超声10min,重复三次后取出放入真空干燥箱中以80℃干燥30min后取出。
经测试,合成的样品具有和实施例1样品相当的催化性能。
由上述实施例可知,本发明制备的多级结构的三元金属硫化物三维电极具有很好的可重复性且优异的催化稳定性。
可以理解的是,以上关于本发明的具体描述,仅用于说明本发明而并非受限于本发明实施例所描述的技术方案。本领域的普通技术人员应当理解,仍然可以对本发明进行修改或等同替换,以达到相同的技术效果;只要满足使用需要,都在本发明的保护范围之内。
Claims (10)
1.一种多级结构的三元金属硫化物三维电极的制备方法,其特征在于:所述制备方法包括如下步骤:
将六水硝酸镍,六水硝酸钴,氟化铵和尿素加入水中形成混合水溶液,然后将泡沫镍置于混合水溶液中进行水热合成镍钴前驱物,最后将制备好的镍钴前驱物进浸入50mM FeCl3溶液中10min,随后取出再放入80℃烘箱中干燥1h,得到FeOOH修饰的镍钴前驱物;
将FeOOH修饰的镍钴前驱物和P2S5依次放置在管式炉的下游和上游的两个单独的瓷舟中,在惰性气氛中进行煅烧,经过洗涤处理得到具有多级结构的三元金属硫化物三维电极。
2.根据权利要求1所述的一种多级结构的三元金属硫化物三维电极的制备方法,其特征在于:所述混合水溶液中,六水硝酸钴的浓度为28-30mg/mL,六水硝酸镍的浓度为28-30mg/mL,氟化铵的浓度为1.8-2.0mg/mL,尿素的浓度为5-7mg/mL。
3.根据权利要求1所述的一种多级结构的三元金属硫化物三维电极的制备方法,其特征在于:所述泡沫镍在使用前进行预处理,所述预处理是将泡沫镍依次经丙酮、乙醇、去离子水交替清洗3次,然后在酸性溶液中浸泡,再用去离子水和乙醇充分清洗,干燥并储存于惰性气氛中。
4.根据权利要求3所述的一种多级结构的三元金属硫化物三维电极的制备方法,其特征在于:所述酸溶液采用稀盐酸或者稀硫酸,且所述酸溶液的浓度为0.05-0.1mol/L。
5.根据权利要求1所述的一种多级结构的三元金属硫化物三维电极的制备方法,其特征在于:所述水热合成是将泡沫镍置于六水硝酸镍,六水硝酸钴,氟化铵和尿素的混合水溶液加热处理,所述水热反应的温度为120℃,反应时间为6-8h,反应溶液体积占水热釜容积的50-70%。
6.根据权利要求1所述的一种多级结构的三元金属硫化物三维电极的制备方法,其特征在于:所述FeOOH修饰的镍钴前驱物与P2S5不直接接触,其两者的距离为2-3cm,所述FeOOH修饰的镍钴前驱物与P2S5的质量比为3-6:1。
7.根据权利要求1所述的一种多级结构的三元金属硫化物三维电极的制备方法,其特征在于:所述瓷舟为石英、Al2O3、Si3N4或BN材质的高温瓷舟。
8.根据权利要求1所述的一种多级结构的三元金属硫化物三维电极的制备方法,其特征在于:所述煅烧的具体步骤包括:将瓷舟置于耐高温的石英管中,充入惰性气体,待通入惰性气体5-10min后完全充满石英管及瓷舟,将石英管放入高温管式炉中进行煅烧,且所述煅烧以10℃/min的升温速率在260-280℃煅烧2h,然后以5℃/min的降温速率降至室温,且所述石英管保持干燥;所述惰性气体采用氮气、氦气和氩气中的任意一种或多种,且所述惰性气体的纯度为99.99%,且所述惰性气体的流速为1-3sccm/s。
9.根据权利要求1所述的一种多级结构的三元金属硫化物三维电极的制备方法,其特征在于:煅烧得到的覆盖有FeCoNiSx样品的所述泡沫镍三维电极取出并进行洗涤;所述洗涤是将样品在蒸馏水、乙醇溶液中交替清洗3次,然后干燥,且所述洗涤的具体处理方式为:将样品放入蒸馏水中超声清洗10-30min,再放入乙醇中超声清洗10-30min,之后取出放入50-80℃真空干燥箱中干燥30min,得到所述具有多级结构的三元金属硫化物三维电极。
10.一种如权利要求1-9任一一项所述的方法制备的多级结构的三元金属硫化物三维电极,即FeCoNiSx/NF双功能电极材料。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114164451A (zh) * | 2021-10-31 | 2022-03-11 | 吉林大学 | 一种磷化物异质纳米片及其制备方法 |
CN118292046A (zh) * | 2024-06-06 | 2024-07-05 | 四川省产品质量监督检验检测院 | 一种自支撑金属硫化物纳米催化材料及其在电解制氢的应用 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110195235A (zh) * | 2019-06-21 | 2019-09-03 | 盐城工学院 | 一种磷掺杂钴酸镍/泡沫镍电极及其制备方法和应用 |
CN111389430A (zh) * | 2020-05-15 | 2020-07-10 | 郑州大学 | 一种电解水制氢用催化剂CoPxSy/MWCNTs及其制备方法 |
CN112774704A (zh) * | 2019-11-07 | 2021-05-11 | 天津大学 | 泡沫镍自支撑FeCo磷化物电催化剂及其制备方法和应用 |
CN112877712A (zh) * | 2021-01-13 | 2021-06-01 | 吉林大学 | 一种过渡金属磷硫化物及其制备方法和应用 |
CN112962115A (zh) * | 2021-02-09 | 2021-06-15 | 上海交通大学 | 一种泡沫镍负载的硫化物电催化剂及其制备方法与应用 |
-
2022
- 2022-04-11 CN CN202210373232.6A patent/CN114855205B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110195235A (zh) * | 2019-06-21 | 2019-09-03 | 盐城工学院 | 一种磷掺杂钴酸镍/泡沫镍电极及其制备方法和应用 |
CN112774704A (zh) * | 2019-11-07 | 2021-05-11 | 天津大学 | 泡沫镍自支撑FeCo磷化物电催化剂及其制备方法和应用 |
CN111389430A (zh) * | 2020-05-15 | 2020-07-10 | 郑州大学 | 一种电解水制氢用催化剂CoPxSy/MWCNTs及其制备方法 |
CN112877712A (zh) * | 2021-01-13 | 2021-06-01 | 吉林大学 | 一种过渡金属磷硫化物及其制备方法和应用 |
CN112962115A (zh) * | 2021-02-09 | 2021-06-15 | 上海交通大学 | 一种泡沫镍负载的硫化物电催化剂及其制备方法与应用 |
Non-Patent Citations (1)
Title |
---|
WANQING TENG ET AL.: ""FeCoNi Sulfides Derived From In situ Sulfurization of Precursor Oxides as Oxygen Evolution Reaction Catalyst"", 《FRONTIERS IN CHEMISTRY》, vol. 8, pages 1 - 8 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114164451A (zh) * | 2021-10-31 | 2022-03-11 | 吉林大学 | 一种磷化物异质纳米片及其制备方法 |
CN114164451B (zh) * | 2021-10-31 | 2022-12-02 | 吉林大学 | 一种磷化物异质纳米片及其制备方法 |
CN118292046A (zh) * | 2024-06-06 | 2024-07-05 | 四川省产品质量监督检验检测院 | 一种自支撑金属硫化物纳米催化材料及其在电解制氢的应用 |
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