CN107034663A - 一种二硫化钨/碳纳米纤维复合材料及其制备方法和用途 - Google Patents
一种二硫化钨/碳纳米纤维复合材料及其制备方法和用途 Download PDFInfo
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Abstract
本发明提供了一种二硫化钨/碳纳米纤维复合材料及其制备方法和用途，制备步骤如下：(1)在高速搅拌和油浴条件下，配制聚丙烯腈纺丝溶液；(2)采用静电纺丝法制备聚丙烯腈纳米纤维；(3)通过程序控温，对步骤(2)的聚丙烯腈纳米纤维进行预氧化处理；(4)通过阶段升温，对步骤(3)的预氧化处理的聚丙烯腈纳米纤维进行碳化处理；(5)将一定量的二硫化钨前驱体化合物加入溶剂中，超声得到二硫化钨前驱体溶液；(6)将碳纳米纤维膜浸入二硫化钨前驱体溶液中，接着置于高压反应釜中，在一定温度下进行溶剂热反应，得到二硫化钨/碳纳米纤维复合材料。本发明制备过程简单，易于操作，所用的聚合物及试剂均环境友好。
Description
技术领域
本发明属于功能化复合碳纳米材料领域，具体为一种二硫化钨/碳纳米纤维复合材料及其制备方法。
背景技术
随着化石能源的日益减少和极端气候的频发，全世界的科学工作者们都致力于开发可再生、低成本和环境友好的能源存储与转换技术，并以此来满足移动电子设备和新能源汽车的快速发展所带来的能源需求。其中，超级电容器、燃料电池、锂离子电池被认为是目前最具发展前景的三种电化学能源存储与转换系统。决定这些新能源体系性能的关键，则在于高性能电极材料和催化剂材料的设计与开发。而为了促进这类新能源技术的产业化，寻找绿色、低成本的非贵金属基材料也是研究者们重点关注的方向。
最近，一种新型的层状过渡金属硫族化合物因为其独特的电化学活性而成为研究热点。作为类石墨烯的新型二维材料，它有着特殊的X-M-X(M＝钼、钨等，X＝硫、硒、碲)层状结构，层间靠弱的范德华力相互作用，层内则靠强的共价键结合，这类材料有着可调的能带结构和优异的电化学性能，在能源存储与转换领域有着潜在的应用价值。大量研究工作显示，少片层的二硫化钨纳米片具有很高的析氢催化性能，在用作析氢催化剂时表现出极高的活性和长循环寿命。理论模拟和实验研究也表明，二硫化钨片层边缘暴露的硫原子有着非常高的电化学活性，而少片层或单片层的结构又进一步增大了活性硫原子的密度。但是在实际应用中二硫化钨纳米片常常存在着易团聚和导电性差的问题，这都很大程度上抑制了该材料的性能表现。由此可见，若要提高二硫化钨的电化学活性需要考虑两点：(1)让二硫化钨暴露更多的活性边缘，或者充分利用其纳米效应，减小其尺寸来提高材料的活性位点密度；(2)通过与导电性好的材料进行复合来增强二硫化钨复合材料的导电性。
静电纺丝是一种能够简单、高效地制备连续纳米纤维的方法，其产物直径一般在10nm到几个微米。利用静电纺丝(如聚丙烯腈polyacrylonitrile(PAN)或聚酰亚胺polyimide(PI)的电纺纳米纤维)结合高温碳化处理可以很便捷地制备碳纳米纤维膜。由于电纺碳纳米纤维膜的高机械强度、良好的导电性、化学稳定性和柔韧性，其在电池电极材料、超级电容器、燃料电池、传感器、催化剂和可穿戴电子器件等领域应用非常广泛。故本发明以电纺制备的自支撑碳纳米纤维膜为柔性基板，利用溶剂热法在其表面上载二硫化钨纳米片，通过纳米纤维多孔的交联网络来实现纳米材料的均匀分散，同时导电性良好的碳纳米纤维基板还能大幅提高复合材料的导电性能，两方面同时增强二硫化钨/碳纳米纤维复合材料的电化学性能。
发明内容
本发明的目的在于提供一种柔性、自支撑的二硫化钨/碳纳米纤维复合材料及其制备方法。
本发明利用静电纺丝技术结合高温碳化制备的碳纳米纤维膜为导电、自支撑模板，通过简单的溶剂热法，制备得到新型的二硫化钨/碳纳米纤维复合材料。
本发明是通过如下技术方案实现的：
一种二硫化钨/碳纳米纤维复合材料，所述二硫化钨/碳纳米纤维复合材料是由二硫化钨纳米片与碳纳米纤维复合而成的，所述二硫化钨纳米片呈竖立姿态均匀生长在碳纳米纤维上。
一种二硫化钨/碳纳米纤维复合材料的制备方法，步骤如下：
(1)在高速搅拌和油浴条件下，配制聚丙烯腈纺丝溶液；
(2)采用静电纺丝法制备聚丙烯腈纳米纤维；
(3)通过程序控温，对步骤(2)的聚丙烯腈纳米纤维进行预氧化处理；
(4)通过阶段升温，对步骤(3)的预氧化处理的聚丙烯腈纳米纤维进行碳化处理；
(5)将一定量的二硫化钨前驱体化合物加入溶剂中，超声得到二硫化钨前驱体溶液；
(6)将步骤(4)得到的碳纳米纤维膜浸入步骤(5)得到的二硫化钨前驱体溶液中，接着置于高压反应釜中，在一定温度下进行溶剂热反应，得到二硫化钨/碳纳米纤维复合材料。
本发明步骤(1)中所述的配制聚丙烯腈纺丝溶液的溶剂为N,N-二甲基甲酰胺，聚丙烯腈纺丝溶液的浓度为0.1～0.2g/mL；所述油浴的温度为75～85℃。
本发明步骤(2)中，所述的静电纺丝法的工艺参数为：流速0.15～0.35mm/min，电压为17～25kV，接收距离为12～20cm。
本发明步骤(3)中，所述的程序控温，气氛为空气，升温速率为1～2℃/min，平台温度为230～300℃，保持2～4h，然后自然降温。
本发明步骤(4)中，所使用的阶段升温程序为：以2～5℃/min的速率从50℃升温至400～500℃，保温50～80min；以5～10℃/min的速率从400～500℃升温至800～1000℃，保温50～80min；自然降温至室温。
本发明步骤(5)中，所述的二硫化钨前驱体化合物为四硫代钨酸铵，溶剂为N,N-二甲基甲酰胺，前驱体溶液浓度为2～5mg/mL。
本发明步骤(6)中，所述的碳纳米纤维膜的加入量为10～30mg每20mL反应溶液，溶剂热反应的温度为200～240℃，时间为10～20h。
本发明所制备的二硫化钨/碳纳米纤维复合材料具有大量暴露的活性位点、丰富的孔隙和良好的导电性能，可作为电化学催化剂、超级电容器电极材料以及锂离子电池等新能源器件的电极材料。
本发明涉及了四个基本原理：
(1)选择聚丙烯腈作为原料来制备电纺碳纳米纤维是因为其良好的可纺性和较高的碳产率；
(2)对聚丙烯腈纳米纤维的预氧化处理可将聚丙烯腈的线性分子结构转化为稳定的梯形结构，有利于纤维在碳化过程中保持稳定的形态；
(3)溶剂热反应过程中，四硫代钨酸铵发生以下反应(NH4)2WS4→2NH3+H2S+S+WS2。
(4)电纺碳纳米纤维的高孔隙率和大比表面积为二硫化钨纳米片的生长提供了大量的成核位点，极大地分散了其均匀生长。
有益效果
(1)本发明制备过程简单，易于操作，所用的聚合物及试剂均环境友好。
(2)设计思路巧妙，以自支撑的电纺碳纳米纤维膜为生长模板，成功解决了纳米材料易团聚的难题；碳纳米纤维基底还增强了复合材料的导电性。
(3)所制备的二硫化钨/碳纳米纤维复合材料适合应用于电化学催化剂、超级电容器电极材料以及锂离子电池等新能源器件的电极材料。
(4)选择聚丙烯腈作为原料来制备电纺碳纳米纤维是因为其良好的可纺性和较高的碳产率
(5)电纺碳纳米纤维的高孔隙率和大比表面积为二硫化钨纳米片的生长提供了大量的成核位点，极大地分散了其均匀生长。
附图说明
图1是碳纳米纤维与四硫代钨酸铵在不同质量比时所得二硫化钨/碳纳米纤维复合材料的电镜照片：(A)1:2，(B)1:6，(C)1:10，(D)未加碳纳米纤维。
图2是碳纳米纤维与四硫代钨酸铵在质量比为1:6时所得二硫化钨/碳纳米纤维复合材料的低倍电镜图。
图3是碳纳米纤维与四硫代钨酸铵在质量比为1:6时所得二硫化钨/碳纳米纤维复合材料的元素分布图。
图4是碳纳米纤维与四硫代钨酸铵在质量比为1:6时所得二硫化钨/碳纳米纤维复合材料的X射线衍射谱图。
具体实施方式
下面结合具体实例，进一步阐述本发明，应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明做各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
本实施例包括以下步骤：
称取1.2g聚丙烯腈粉末加入10mL DMF中，在85℃油浴加热下高速搅拌8h后得到澄清的聚丙烯腈溶液。对上述聚丙烯腈溶液进行静电纺丝，设置纺丝参数为：流速0.28mm/min，电压为22kV，接收距离为18cm。制备的聚丙烯腈纳米纤维最终以纳米纤维膜的形式沉积在滚筒接收器上，将纤维膜揭下并置于真空干燥箱内保存24h以除去残余DMF。干燥的聚丙烯腈纤维膜固定在平板上并转移至程序控温烘箱中进行预氧化处理，以1.5℃/min的升温速率从室温升至250℃并保持2.5h，然后自然降至室温，预氧化处理后的聚丙烯腈纤维膜颜色变为深棕色。将预氧化的聚丙烯腈纳米纤维置于程序控温管式炉中进行高温碳化处理，以2.5℃/min的升温速率从50℃升温至400℃，保温60min，接着以10℃/min的速率从400℃升温至800℃，保温60min后自然降温，得到黑色的电纺碳纳米纤维。
称取60mg四硫代钨酸铵粉末，加入30mL DMF中，超声并搅拌之后得到浓度为2mg/mL的四硫代钨酸铵溶液。称取30mg碳纳米纤维膜加入上述溶液中，一并转移至聚四氟乙烯内衬的反应釜中，在200℃烘箱中反应12h后取出，将产物进行清洗、烘干，便得到二硫化钨/碳纳米纤维复合膜材料。
使用场发射扫描电子显微镜(FESEM)、能谱仪(EDS)和X射线衍射(XRD)来表征本发明所获得的二硫化钨/碳纳米纤维复合材料的形貌与组成，其结果如下：
(1)随着溶剂热反应中碳纳米纤维与四硫代钨酸铵在质量比由1:2、1:6、1:10逐渐增大时，二硫化钨纳米片在碳纳米纤维上的生长呈现出逐渐密集的趋势，且在两者质量比为1:6时二硫化钨的分布最为均匀，纳米片呈竖立姿态均匀生长在每根碳纳米纤维上。质量比为1:10时二硫化钨会出现较严重的团聚，参见图1(A-C)以及图2。
(2)当不使用碳纳米纤维作为生长模板时，二硫化钨呈现出球状的团聚体形态，说明了碳纳米纤维在分散二硫化钨均匀生长中起到的重要作用，参见图1(D)。
(3)溶剂热反应中碳纳米纤维与四硫代钨酸铵在质量比为1:6时，所得的二硫化钨/碳纳米纤维复合材料其表面有着明显的碳、钨、硫的元素分布，参见图3。
(4)溶剂热反应中碳纳米纤维与四硫代钨酸铵在质量比为1:6时，所得的二硫化钨/碳纳米纤维复合材料的X射线衍射谱图中显示出归属于二硫化钨的一系列特征峰：(002)、(004)、(100)、(105)、(110)，参见图4。
实施例2
本实施例包括以下步骤：
制备电纺碳纳米纤维膜的步骤同实施例1。
分别称取180mg、300mg四硫代钨酸铵加入30mL DMF中，超声并搅拌之后配置浓度分别为6mg/mL和10mg/mL的四硫代钨酸铵溶液。称取两块30mg碳纳米纤维膜分别加入上述两种溶液中，转移至聚四氟乙烯内衬的反应釜中，在200℃烘箱中反应12h后取出，将产物进行清洗、烘干，便得到上载量更大的两种二硫化钨/碳纳米纤维复合膜材料。
实施例3
本实施例包括以下步骤：
称取60mg四硫代钨酸铵粉末，加入30mL DMF中，超声并搅拌之后得到浓度为2mg/mL的四硫代钨酸铵溶液。将上述溶液转移至聚四氟乙烯内衬的反应釜中，在200℃烘箱中反应12h后取出，将产物进行离心、清洗、烘干，便得到纯的二硫化钨。
Claims (9)
1.一种二硫化钨/碳纳米纤维复合材料，其特征在于，所述二硫化钨/碳纳米纤维复合材料是由二硫化钨纳米片与碳纳米纤维复合而成的，所述二硫化钨纳米片呈竖立姿态均匀生长在碳纳米纤维上。
2.如权利要求1所述的一种二硫化钨/碳纳米纤维复合材料的制备方法，其特征在于，步骤如下：
(1)在高速搅拌和油浴条件下，配制聚丙烯腈纺丝溶液；
(2)采用静电纺丝法制备聚丙烯腈纳米纤维；
(3)通过程序控温，对步骤(2)的聚丙烯腈纳米纤维进行预氧化处理；
(4)通过阶段升温，对步骤(3)的预氧化处理的聚丙烯腈纳米纤维进行碳化处理，得到碳纳米纤维膜；
(5)将一定量的二硫化钨前驱体化合物加入溶剂中，超声得到二硫化钨前驱体溶液；
(6)将步骤(4)得到的碳纳米纤维膜浸入步骤(5)得到的二硫化钨前驱体溶液中，接着置于高压反应釜中，在一定温度下进行溶剂热反应，得到二硫化钨/碳纳米纤维复合材料。
3.如权利要求2所述的一种二硫化钨/碳纳米纤维复合材料的制备方法，其特征在于，步骤(1)中所述的配制聚丙烯腈纺丝溶液的溶剂为N,N-二甲基甲酰胺，聚丙烯腈纺丝溶液的浓度为0.1～0.2g/mL；所述油浴的温度为75～85℃。
4.如权利要求2所述的一种二硫化钨/碳纳米纤维复合材料的制备方法，其特征在于，步骤(2)中，所述的静电纺丝法的工艺参数为：流速0.15～0.35mm/min，电压为17～25kV，接收距离为12～20cm。
5.如权利要求2所述的一种二硫化钨/碳纳米纤维复合材料的制备方法，其特征在于，步骤(3)中，所述的程序控温，气氛为空气，升温速率为1～2℃/min，平台温度为230～300℃，保持2～4h，然后自然降温。
6.如权利要求2所述的一种二硫化钨/碳纳米纤维复合材料的制备方法，其特征在于，步骤(4)中，所使用的阶段升温程序为：以2～5℃/min的速率从50℃升温至400～500℃，保温50～80min；以5～10℃/min的速率从400～500℃升温至800～1000℃，保温50～80min；自然降温至室温。
7.如权利要求2所述的一种二硫化钨/碳纳米纤维复合材料的制备方法，其特征在于，步骤(5)中，所述的二硫化钨前驱体化合物为四硫代钨酸铵，溶剂为N,N-二甲基甲酰胺，前驱体溶液浓度为2～5mg/mL。
8.如权利要求2所述的一种二硫化钨/碳纳米纤维复合材料的制备方法，其特征在于，步骤(6)中，所述的碳纳米纤维膜的加入量为10～30mg每20mL反应溶液，溶剂热反应的温度为200～240℃，时间为10～20h。
9.权利要求2～8任意一项所述的方法制备的二硫化钨/碳纳米纤维复合材料的用途，其特征在于，所述二硫化钨/碳纳米纤维复合材料用作电化学催化剂、超级电容器电极材料以及锂离子电池的电极材料。
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| CN111463443A (zh) * | 2020-03-28 | 2020-07-28 | 旌德君创科技发展有限公司 | 一种Pt-WS2@碳布复合催化剂及其制备方法 |
| CN112837941A (zh) * | 2021-01-13 | 2021-05-25 | 巫国家 | 一种活性碳纤维多孔二硫化钨纳米复合材料的制备方法 |
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