CN110504431B - 一种二硫化钼/石墨烯/碳复合材料及其应用 - Google Patents

一种二硫化钼/石墨烯/碳复合材料及其应用 Download PDF

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CN110504431B
CN110504431B CN201910804766.8A CN201910804766A CN110504431B CN 110504431 B CN110504431 B CN 110504431B CN 201910804766 A CN201910804766 A CN 201910804766A CN 110504431 B CN110504431 B CN 110504431B
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graphene
molybdenum disulfide
composite material
carbon
pore
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段雅静
杜辉
付慧
陈照军
付金喆
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Qingdao University
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Abstract

本发明属于碳复合材料技术领域，公开了一种具有多级孔结构的二硫化钼/石墨烯/碳复合材料，由直径为60～500nm的复合纳米纤维构成，以质量百分数计，复合纳米纤维中含二硫化钼3％～35％，含石墨烯0.2％～10％，含碳60％～95％；复合纳米纤维沿轴向分布有多级孔结构，孔径在0.1nm～5μm之间连续分布，平均孔径为1.5nm～25nm，以孔体积计，多级孔结构中微孔结构占25％～60％、介孔结构占40％～75％，微孔结构分布在纳米纤维表面和介孔结构的孔壁上；复合材料具有高比表面积、孔隙结构发达、孔道尺寸和结构可控、应用广泛等优点。

Description

一种二硫化钼/石墨烯/碳复合材料及其应用
技术领域
本发明属于碳复合材料领域，特别涉及一种具有多级孔结构的二硫化钼/石墨烯/碳复合材料及其应用。
背景技术
多孔碳材料因具有高比表面积、高孔隙率、良好的导电性和导热性、可调控的孔径和表面性能，在催化剂载体、超级电容器、催化剂、吸附剂和气体储存等领域有广泛应用。自2004年单层石墨烯被发现以来，以其为代表的各类二维材料由于具有丰富多样的物理、化学性质，并且在电子器件、光电器件、催化、能源和环境等领域表现出广阔的应用前景而受到研究人员的广泛关注。单层二硫化钼是一种具有和石墨烯类似结构的过渡金属层状化合物，原来多用作固体润滑剂和加氢催化剂，随着人们对二硫化钼二维材料认知的深入，其一系列独特的物理化学性质逐渐被人们所发现，在微电子、传感、能源、环境等领域表现出极大的应用前景。但是，纯二硫化钼易于团聚，使其活性位点无法得到充分暴露，严重影响了其催化特性和能量存储的循环稳定性。因此，将二硫化钼与稳定性优异的碳纳米材料进行有效复合具有重要意义。
中国发明专利201711384891.5公开了一种具有三级结构的泡沫石墨烯/碳纳米管/二硫化钼复合材料，其结构特征包括三维泡沫石墨烯一级结构，在其上原位生长有一维碳纳米管二级结构，又在二级结构上包覆有二维二硫化钼三级结构。碳基材料组成的一级和二级结构决定了此复合材料具有高比表面，非碳材料二硫化钼组成的三级结构决定了此复合材料具有高催化活性。碳纳米管在三维泡沫石墨烯一级结构上原位生长，确保了三维骨架结构的完整性，三级结构的二维二硫化钼覆盖于碳材料表面，保护了碳材料，解决了碳材料的不稳定问题，且二硫化钼三级结构只有几个原子厚度，克服了非碳材料质量较重、价格昂贵、导电性差的缺陷。但该复合材料只是简单的具有固定的三层结构，并未形成多级孔结构。
中国发明专利201510947452.5公开了一种二硫化钼/石墨烯/碳纳米纤维复合材料，首先通过静电纺丝制备得到聚丙烯腈纳米纤维膜，经过溶液浸泡法在聚丙烯腈纳米纤维上包裹氧化石墨烯，再通过高温碳化制备得到石墨烯/碳纳米纤维复合膜，最后通过一步水热法在石墨烯/碳纳米纤维上原位生长二硫化钼纳米片。该发明所制备的二硫化钼/石墨烯/碳纳米纤维复合材料是一种复合碳纤维膜材料，其纤维结构中不存在内部孔道，其比表面积较小，能够暴露出的活性点位较少，影响其应用性能。
中国专利201510245973.6提供一种三维大孔石墨烯-碳纳米管-二硫化钼复合材料，是由孔径为0.1mm～5mm的泡沫金属经预处理及化学气相沉积，得到三维大孔石墨烯/泡沫金属复合物，然后将三维大孔石墨烯/泡沫金属复合物置于硝酸镍及氯化钴的水溶液中，烘干，化学气相沉积，得到三维大孔石墨烯/碳纳米管/泡沫金属复合物，将三维大孔石墨烯/碳纳米管/泡沫金属复合物浸渍于刻蚀液中，得到三维大孔石墨烯/碳纳米管，利用水热法在三维大孔石墨烯/碳纳米管上负载二硫化钼，得到负载有二硫化钼的三维大孔石墨烯/碳纳米管，最后退火负载有二硫化钼的三维大孔石墨烯/碳纳米管，得到三维大孔石墨烯-碳纳米管-二硫化钼复合材料；作为锂离子电池负极活性材料，具有容量高、稳定性好的优点，但其孔结构单一，制备工艺复杂。
中国专利201410711472.8公开了一种三维多孔类石墨烯负载二硫化钼复合材料，是由三维多孔类石墨烯网络及在该三维多孔类石墨烯网络表面负载二硫化钼纳米片构成，其中，三维多孔石墨烯厚度为1～20nm，网络半径为1～15nm，应用于锂离子电池负极材料。该材料主要是利用了石墨烯的三维多孔结构，并未在整个材料结构中形成多级孔结构。
现有的石墨烯/二硫化钼类碳复合材料孔径结构单一，大部分只是简单利用了石墨烯的孔结构特征，内部孔道结构缺乏，且复合材料的孔径结构不可调控，严重限制了多孔碳材料的应用面和应用效果。而只有可调控的多孔碳材料才可以根据需求形成不同孔径的结构，才可以分别满足在催化剂载体、超级电容器、催化剂、吸附剂和气体储存等领域中的应用。
发明内容
本发明的目的在于克服现有技术存在的缺点，提出一种具有多级孔结构的二硫化钼/石墨烯/碳复合材料及其应用，所述的二硫化钼/石墨烯/碳复合材料具有高比表面积、孔隙结构发达、孔道尺寸和结构可控、应用广泛等优点。
本发明是采用以下的技术方案实现的：
一种二硫化钼/石墨烯/碳复合材料，所述复合材料是由直径为60～500nm的复合纳米纤维构成，以质量百分数计，复合纳米纤维中含二硫化钼3％～35％，含石墨烯0.2％～10％，含碳60％～95％；复合纳米纤维沿轴向分布有多级孔结构。
优选的，以质量百分数计，复合纳米纤维中含二硫化钼6％～33％，含石墨烯0.6％～7％，含碳60％～94％。
可选的，所述二硫化钼和石墨烯均以单片层结构均匀分散在以碳纳米纤维为基底的复合纳米纤维中。
可选的，所述多级孔的孔径在0.1nm～5μm之间连续分布，平均孔径为1.5nm～25nm。
可选的，以孔体积计，所述多级孔结构中微孔结构占25％～60％、介孔结构占40％～75％。
可选的，所述微孔结构分布在纳米纤维表面和介孔结构的孔壁上。
可选的，所述复合材料的比表面积为500～3200m2/g；
优选的，所述复合材料的比表面积为600～3152m2/g。
进一步，本发明所述的具有多级孔结构的二硫化钼/石墨烯/碳复合材料通过下述方法制得：
(1)称取0.6g～1.5g聚丙烯腈、0.5g～1.2g聚乙烯吡咯烷酮、0.2g～1.0g四硫代钼酸铵和0.05g～0.2g石墨烯，搅拌溶解于10g～16gDMF中，使用400目不锈钢网过滤后备用；
(2)取适量溶液进行静电纺丝，静电纺丝参数如下：纺丝电压为20kV，推进速率为0.015mL/min，纺丝接收距离为18cm，注射器针头为8#，在室温下纺丝2-10h制得复合纤维膜；
(3)将上述复合纤维膜放入管式炉中，在N2/H2(体积比：9/1)混合气氛下，以2～6℃/min的升温速率升温至380～450℃，维持1～6h，然后降温至室温，取出；
(4)配制KOH饱和溶液，按上述处理后的复合纤维膜/KOH质量比为1:0.4～10进行浸渍处理，按比例将上述处理后的复合纤维膜放入KOH饱和溶液中，超声处理1h，然后静置浸渍48h，真空干燥8h；
(5)将上述浸渍后的复合纤维膜放入管式炉中，在氩气气氛下，以2～10℃/min的升温速率升温至750～850℃，高温活化1～16h，降至室温后，取出使用稀盐酸溶液洗涤，真空干燥10h，得到具有多级孔结构的二硫化钼/石墨烯/碳复合纤维材料。
本发明的另一方面，提供了所述二硫化钼/石墨烯/碳复合材料的制备方法。
又一方面，本发明制备的二硫化钼/石墨烯/碳复合材料可广泛应用于锂离子电池负极材料、超级电容器电极材料、水电解制氢催化材料、汞吸附材料等领域。其中，多级孔结构中微孔结构占比大于40％的二硫化钼/石墨烯/碳复合材料，利于锂离子、钾离子、氢离子等小体积离子的传输，适用于锂离子电池负极材料、超级电容器电极材料、水电解制氢催化材料；多级孔结构中微孔结构占比小于40％的二硫化钼/石墨烯/碳复合材料，大量的介孔结构更利于汞离子的扩散，因此更适用于汞吸附材料。
本发明首先通过静电纺丝法纺制聚丙烯腈/聚乙烯吡咯烷酮/四硫代钼酸铵/石墨烯复合纤维膜；然后在380～450℃下高温处理，聚乙烯吡咯烷酮经高温分解，沿纤维轴向形成大量的介孔结构，通过调整聚丙烯腈与聚乙烯吡咯烷酮的比例，即可调控复合纤维中介孔结构的尺寸；同时四硫代钼酸铵高温分解为单片层二硫化钼分散在纤维中；使用KOH饱和溶液对上述高温处理后的复合纤维膜进行超声浸渍和静置浸渍，使KOH浸渍在复合纤维膜的表面及纤维的介孔结构中，然后进行高温活化，在纤维表面和介孔结构的孔壁上进一步生成大量的微孔结构，通过控制KOH的用量和高温活化条件，来调控复合纤维中微孔结构的尺寸；清洗干燥后最终得到具有多级孔结构的二硫化钼/石墨烯/碳复合材料。采用本发明所述的制备方法，可以灵活调节多级孔结构中介孔结构和微孔结构的比例。
与现有技术相比，本发明的技术方案具有以下优点和进步：
本发明提供的具有多级孔结构的二硫化钼/石墨烯/碳复合材料的孔隙结构发达、孔道尺寸和结构可控、比表面积高，结构均一，形貌优良，且制备工艺简单，应用前景广阔，能够广泛应用于催化、环境、能源等领域。
附图说明
图1为具有多级孔结构的二硫化钼/石墨烯/碳复合纳米纤维结构示意图，其中1为复合纳米纤维，2为介孔结构，3为微孔结构。
图2为具有多级孔结构的二硫化钼/石墨烯/碳复合纳米纤维的切面结构示意图，其中1为复合纳米纤维，2为介孔结构，3为微孔结构。
图3为实施例2所制备多级孔结构的二硫化钼/石墨烯/碳复合材料的扫描电镜照片。
图4为实施例2所制备多级孔结构的二硫化钼/石墨烯/碳复合材料中纤维横截面的扫描电镜照片。
图5为实施例2所制备多级孔结构的二硫化钼/石墨烯/碳复合材料的透射电镜照片。
具体实施方式
下面结合实施例对本发明的实施方案进行详细描述，实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器均为可以通过市售购买获得的常规产品。
实施例1
称取0.6g聚丙烯腈、0.5g聚乙烯吡咯烷酮、0.3g四硫代钼酸铵和0.05g石墨烯，搅拌溶解于12gDMF中，使用400目不锈钢网过滤后备用；取适量溶液进行静电纺丝，静电纺丝参数为纺丝电压为20kV、推进速率为0.015mL/min、纺丝接收距离为18cm、注射器针头为8#，在室温下纺丝4h制得复合纤维膜；将上述复合纤维膜放入管式炉中，在N2/H2(体积比：9/1)混合气氛下，以2℃/min的升温速率升温至400℃，维持4h，然后降温至室温，取出；配制KOH饱和溶液，按上述处理后的复合纤维膜/KOH质量比为1:5进行浸渍处理，按比例将上述处理后的复合纤维膜放入KOH饱和溶液中，超声处理1h，然后静置浸渍48h，真空干燥8h；将上述浸渍后的复合纤维膜放入管式炉中，在氩气气氛下，以2℃/min的升温速率升温至750℃，高温活化2h，降至室温后，取出使用稀盐酸溶液洗涤，真空干燥10h，得到具有多级孔结构的二硫化钼/石墨烯/碳复合材料。该产品由直径为80～300nm的复合纳米纤维构成，以质量百分数计，该产品中含二硫化钼6％，含石墨烯0.6％，含碳93.4％；该产品的比表面积为600m2/g，孔径在0.1nm～5μm之间连续分布，平均孔径为1.6nm，其孔道结构中微孔结构占58％、介孔结构占42％。该产品可用于锂离子电池负极材料、超级电容器电极材料、水电解制氢催化材料等。
实施例2
称取1.5g聚丙烯腈、1.0g聚乙烯吡咯烷酮、0.8g四硫代钼酸铵和0.2g石墨烯，搅拌溶解于16gDMF中，使用400目不锈钢网过滤后备用；取适量溶液进行静电纺丝，静电纺丝参数为纺丝电压为20kV、推进速率为0.015mL/min、纺丝接收距离为18cm、注射器针头为8#，在室温下纺丝2h制得复合纤维膜；将上述复合纤维膜放入管式炉中，在N2/H2(体积比：9/1)混合气氛下，以6℃/min的升温速率升温至450℃，维持1h，然后降温至室温，取出；配制KOH饱和溶液，按上述处理后的复合纤维膜/KOH质量比为1:0.5进行浸渍处理，按比例将上述处理后的复合纤维膜放入KOH饱和溶液中，超声处理1h，然后静置浸渍48h，真空干燥8h；将上述浸渍后的复合纤维膜放入管式炉中，在氩气气氛下，以8℃/min的升温速率升温至850℃，高温活化15h，降至室温后，取出使用稀盐酸溶液洗涤，真空干燥10h，得到具有多级孔结构的二硫化钼/石墨烯/碳复合材料。该产品由直径为60～420nm的复合纳米纤维构成，以质量百分数计，该产品中含二硫化钼33％，含石墨烯7％，含碳60％；该产品的比表面积为2522m2/g，孔径在0.1nm～5μm之间连续分布，平均孔径为12.6nm，其孔道结构中微孔结构占37％、介孔结构占63％。该产品可用于汞吸附材料。
图3和图4为本实施例制得的二硫化钼/石墨烯/碳复合材料的扫描电镜照片，可以看出纤维中沿轴向具有不同尺寸的介孔结构，纤维表面和介孔结构孔壁上分布有大量微孔结构。图5为本实施例制得的二硫化钼/石墨烯/碳复合材料的透射电镜照片，可以看出二硫化钼和石墨烯均是以单片层结构高度均匀分散在复合纤维中。
实施例3
称取1.0g聚丙烯腈、1.2g聚乙烯吡咯烷酮、1.0g四硫代钼酸铵和0.1g石墨烯，搅拌溶解于10gDMF中，使用400目不锈钢网过滤后备用；取适量溶液进行静电纺丝，静电纺丝参数为纺丝电压为20kV、推进速率为0.015mL/min、纺丝接收距离为18cm、注射器针头为8#，在室温下纺丝10h制得复合纤维膜；将上述复合纤维膜放入管式炉中，在N2/H2(体积比：9/1)混合气氛下，以4℃/min的升温速率升温至380℃，维持6h，然后降温至室温，取出；配制KOH饱和溶液，按上述处理后的复合纤维膜/KOH质量比为1:10进行浸渍处理，按比例将上述处理后的复合纤维膜放入KOH饱和溶液中，超声处理1h，然后静置浸渍48h，真空干燥8h；将上述浸渍后的复合纤维膜放入管式炉中，在氩气气氛下，以10℃/min的升温速率升温至800℃，高温活化1h，降至室温后，取出使用稀盐酸溶液洗涤，真空干燥10h，得到具有多级孔结构的二硫化钼/石墨烯/碳复合材料。该产品由直径为150～500nm的复合纳米纤维构成，以质量百分数计，该产品中含二硫化钼14％，含石墨烯6.2％，含碳79.8％；该产品的比表面积为3152m2/g，孔径在0.1nm～5μm之间连续分布，平均孔径为23.6nm，其孔道结构中微孔结构占25.8％、介孔结构占74.2％。该产品可用于汞吸附材料。
实施例4
称取1.3g聚丙烯腈、0.6g聚乙烯吡咯烷酮、0.4g四硫代钼酸铵和0.15g石墨烯，搅拌溶解于10gDMF中，使用400目不锈钢网过滤后备用；取适量溶液进行静电纺丝，静电纺丝参数为纺丝电压为20kV、推进速率为0.015mL/min、纺丝接收距离为18cm、注射器针头为8#，在室温下纺丝8h制得复合纤维膜；将上述复合纤维膜放入管式炉中，在N2/H2(体积比：9/1)混合气氛下，以3℃/min的升温速率升温至425℃，维持5h，然后降温至室温，取出；配制KOH饱和溶液，按上述处理后的复合纤维膜/KOH质量比为1:6进行浸渍处理，按比例将上述处理后的复合纤维膜放入KOH饱和溶液中，超声处理1h，然后静置浸渍48h，真空干燥8h；将上述浸渍后的复合纤维膜放入管式炉中，在氩气气氛下，以6℃/min的升温速率升温至820℃，高温活化12h，降至室温后，取出使用稀盐酸溶液洗涤，真空干燥10h，得到具有多级孔结构的二硫化钼/石墨烯/碳复合材料。该产品由直径为60～500nm的复合纳米纤维构成，以质量百分数计，该产品中含二硫化钼9.5％，含石墨烯1.9％，含碳88.6％；该产品的比表面积为1855m2/g，孔径在0.1nm～5μm之间连续分布，平均孔径为4.5nm，其孔道结构中微孔结构占43％、介孔结构占57％。该产品可用于锂离子电池负极材料、超级电容器电极材料、水电解制氢催化材料等。

Claims (9)

1.一种二硫化钼/石墨烯/碳复合材料，其特征在于，所述复合材料是由直径为60～500nm的复合纳米纤维构成，以质量百分数计，复合纳米纤维中含二硫化钼3％～35％，含石墨烯0.2％～10％，含碳60％～95％；复合纳米纤维沿轴向分布有多级孔结构。
2.根据权利要求1所述的一种二硫化钼/石墨烯/碳复合材料，其特征在于，所述二硫化钼和石墨烯均以单片层结构均匀分散在以碳纳米纤维为基底的复合纳米纤维中。
3.根据权利要求1所述的一种二硫化钼/石墨烯/碳复合材料，其特征在于，多级孔结构的孔径在0.1nm～5μm之间连续分布，平均孔径为1.5nm～25nm。
4.根据权利要求1所述的一种二硫化钼/石墨烯/碳复合材料，其特征在于，以孔体积计，多级孔结构中微孔结构占25％～60％、介孔结构占40％～75％。
5.根据权利要求4所述的一种二硫化钼/石墨烯/碳复合材料，其特征在于，所述微孔结构分布在纳米纤维表面和介孔结构的孔壁上。
6.根据权利要求1所述的一种二硫化钼/石墨烯/碳复合材料，其特征在于，所述复合材料的比表面积为500～3200m2/g。
7.根据权利要求1-6任一所述的一种二硫化钼/石墨烯/碳复合材料，其特征在于，通过下述方法制得：
(1)称取0.6g～1.5g聚丙烯腈、0.5g～1.2g聚乙烯吡咯烷酮、0.2g～1.0g四硫代钼酸铵和0.05g～0.2g石墨烯，搅拌溶解于10g～16gDMF中，使用400目不锈钢网过滤后备用；
(2)取适量溶液进行静电纺丝，制得复合纤维膜；
(3)将上述复合纤维膜放入管式炉中，在体积比为9/1的N2/H2混合气氛下，以2～6℃/min的升温速率升温至380～450℃，维持1～6h，然后降温至室温，取出；
(4)配制KOH饱和溶液，按上述处理后的复合纤维膜/KOH质量比为1:0.4～10进行浸渍处理，按比例将上述处理后的复合纤维膜放入KOH饱和溶液中，超声处理1h，然后静置浸渍48h，真空干燥8h；
(5)将上述浸渍后的复合纤维膜放入管式炉中，在氩气气氛下，以2～10℃/min的升温速率升温至750～850℃，高温活化1～16h，降至室温后，取出使用稀盐酸溶液洗涤，真空干燥10h，得到具有多级孔结构的二硫化钼/石墨烯/碳复合材料。
8.根据权利要求7所述的一种二硫化钼/石墨烯/碳复合材料，其特征在于，步骤(2)中所述静电纺丝参数如下：纺丝电压为20kV，推进速率为0.015mL/min，纺丝接收距离为18cm，注射器针头为8#，在室温下纺丝2-10h制得复合纤维膜。
9.权利要求1-8任一所述二硫化钼/石墨烯/碳复合材料在锂离子电池负极材料、超级电容器电极材料、水电解制氢催化材料、汞吸附材料领域中的应用。
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