CN106229155B - 一种制备单层2h相二硫化钼/微纳米碳复合材料的方法 - Google Patents
一种制备单层2h相二硫化钼/微纳米碳复合材料的方法 Download PDFInfo
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- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 65
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 21
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 14
- -1 lithium salt compound Chemical class 0.000 claims abstract description 10
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims abstract description 9
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
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- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 claims description 2
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- IQMAMZYAQFTIAU-UHFFFAOYSA-N lithium;sulfanylidenemolybdenum Chemical compound [Li].[Mo]=S IQMAMZYAQFTIAU-UHFFFAOYSA-N 0.000 description 4
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种制备单层2H相二硫化钼/微纳米碳复合材料的方法，具体过程为：以硫代钼酸铵和锂盐化合物为原料，通过简单的温度控制可以合成为插锂的2H相硫化钼块体，插锂的2H相硫化钼块体可以在水中水解自行剥离成2H相单层MoS2纳米片，再与微纳米碳自组装形成单层2H相二硫化钼/微纳米碳复合材料。本发明工艺操作简单，反应条件温和，所用试剂价格低廉，绿色环保。
Description
技术领域
本发明属于二硫化钼/碳复合材料的合成技术领域，具体涉及一种制备单层2H相二硫化钼/微纳米碳复合材料的方法。
背景技术
二硫化钼具有典型三明治层状结构，由于其层间相对较弱的范德华力，也可以剥离成单层或少层数的纳米片，被认为是另外一种相当重要的二维纳米片材料，具有独特的物理、化学和电学特性。Radisavljevic等人测试表明单层MoS2的电导率要比块体MoS2提高100个数量级，使得其在电子器件及电子传感器中有着优越的性能（Nat.Nanotechnol.2011,6,147）；Mak等人通过计算模拟表明MoS2从块体剥离至单层，由于量子限域效应，其禁带宽度由间接带隙的1.3eV增大为直接带隙的1.8eV，使得光生电子空穴的分离能力提高（Phys.Rev.Lett.2010,105）；Hinnemann等人通过密度函公式计算纳米级MoS2的暴露活性边缘的吸附氢吉布斯自由能，发现其边缘有很强的氢吸附能力，并有着金属Pt一样接近零吉布斯自由能的析氢性能，从而推断出单层的MoS2拥有更多的暴露活性边缘，很有希望成为替代Pt作为析氢材料的催化剂（J.Am.Chem.Soc.2005,127,5308）。ChenW.X.等人研究表明，单层MoS2在与碳基材料复合时，有着超高的容量贡献（>1500mAh/g），远远超过其块体材料的理论值（J.Mater.Chem.2011,21,6251）。
二硫化钼存在三种相态，即1T、2H和3R相。其中，1T相是MoS2以一个S-Mo-S单分子层作为最小重复单元堆叠，而2H和3R相是以两个和三个S-Mo-S单分子层作为最小重复单元堆叠。自然界中大部分MoS2是以2H稳定相存在的，1T和3R相属于亚稳态结构，在一定条件下可以转变为2H相。由于单层2H相的MoS2已经失去了双分子层为最小重复单元的特性，因此也被称为1H相。不同相态的MoS2材料所呈现的物理化学特性也不尽相同。例如，2H态MoS2材料展现出禁带宽度为1.3-1.9eV的半导体特性，其通过层数的多少来调节禁带宽度的大小；而1T态的MoS2材料则呈现出金属特性，其优越的导电性在催化水分解制氢以及超级电容领域取得了重要的突破（Advanced Energy Materials,2016,DOI:10.1002/aenm.201502555）。
虽然单层MoS2纳米材料在热、电、光、力学等方面的性质及其在光电子器件领域的潜在应用引起了科研人员的广泛关注。然而，一般的化学、物理法难以制备出纯单层结构的MoS2纳米材料，尤其是不同相态的单层硫化钼剥离制备。目前制备单层MoS2纳米材料的主要有微机械力剥离法、化学气相沉积法、锂离子插层法以及液相超声法等，这些剥离方法不仅操作繁琐，工艺复杂，而且单层MoS2的产量极低，大部分是厚度为1-100nm的少层数MoS2纳米片，而非真正意义上的单层MoS2。除了难以高效率地剥离制备单层MoS2纳米片外，MoS2纳米片只能在诸如二甲基甲酰胺和N-甲基吡咯烷酮等高沸点有机溶剂中剥离和保存，而这些有机溶剂粘度大、沸点很高，在离心收集过程中，单层或少层数MoS2又重新聚集成多层MoS2纳米片，从而限制了单层MoS2纳米片在一些科研或工业领域的探索和应用。此外，MoS2纳米片在实际应用研究过程中，常与无定型碳、碳纳米管、碳纤维以及石墨烯等碳材料复合，以增加其导电性能。
发明内容
本发明解决的技术问题是提供了一种简单、安全、高效且适合规模化生产的制备单层2H相二硫化钼/微纳米碳复合材料的方法，该方法是以硫代钼酸铵和锂盐化合物为原料，在一定温度下热处理得到2H相的插锂Li2MoS2块体，插锂Li2MoS2块体在去离子水中水解自行剥离，再与添加的微纳米碳自组装成单层2H相二硫化钼/微纳米碳复合材料，制得的单层2H相二硫化钼/微纳米碳复合材料既可以提高材料的导电性能，又可以有效抑制单层2H相二硫化钼的团聚。
本发明为解決上述技术问题采用如下技术方案，一种制备单层2H相二硫化钼/微纳米碳复合材料的方法，其特征在于具体步骤为：
（1）将硫代钼酸铵和锂盐化合物按1:2摩尔比混合研磨，研磨后的混合物在惰性气体保护下于200-400℃保温1-10h，冷却至室温得到插锂的2H相硫化钼块体；
（2）将插锂的2H相硫化钼块体直接置于去离子水中，辅助超声水解剥离5-30min，再将得到的悬浮液置于离心机中，经离心分离去除未剥离的沉淀物后得到单层2H相MoS2纳米片悬浮液；
（3）将微纳米碳加入到单层2H相MoS2纳米片悬浮液中得到混合悬浮液，再加入十六烷基三甲基溴化铵，其中十六烷基三甲基溴化铵的质量与混合悬浮液的体积比为1g:22.5-180mL，然后超声分散10-30min得到单层2H相MoS2/微纳米碳悬浮液；
（4）将得到的单层2H相MoS2/微纳米碳悬浮液在离心机上分别用水和乙醇离心洗涤去除可溶性杂质，最后将沉淀物单层2H相二硫化钼/微纳米碳复合材料分散于小分子溶剂中保存，其中单层2H相MoS2纳米片的厚度小于1nm。
进一步限定，步骤（1）中所述的锂盐化合物为氢氧化锂、氯化锂、醋酸锂、碳酸锂、硫酸锂或硝酸锂中的一种或多种。
进一步限定，步骤（2）中所述的离心机转速为1000r/min，步骤（4）中所述的离心机转速为4000-20000r/min。
进一步限定，步骤（3）中所述的微纳米碳为导电碳黑、纳米碳纤维、碳纳米管、石墨粉或还原氧化石墨烯。
进一步限定，步骤（3）中所述的微纳米碳与单层2H相MoS2纳米片悬浮液中MoS2的质量比为0.005-0.2:1。
进一步限定，步骤（4）中所述的小分子溶剂为水、甲醇、乙醇、异丙醇、丁醇、丙酮、N-甲基吡咯烷酮或N-甲基甲酰胺。
本发明与现有技术相比具有以下优点：
1、本发明以硫代钼酸铵和锂盐化合物为原料，通过简单的温度控制可以合成为插锂的2H相硫化钼块体，插锂的2H相硫化钼块体可以在水中水解自行剥离成2H相单层MoS2纳米片，再与微纳米碳自组装形成单层2H相二硫化钼/微纳米碳复合材料，并且可以在水、乙醇等小分子溶剂中稳定存在；
2、本发明得到的2H相单层MoS2纳米片的厚度小于1nm，而非现有技术中的1-100nm厚度的MoS2纳米片；
3、本发明合成的单层2H相二硫化钼/微纳米碳复合材料可以用于单层硫化钼在光析氢、电催化和储能等领域的研究；
4、本发明工艺操作简单，反应条件温和，所用试剂价格低廉，绿色环保。
具体实施方式
以下通过实施例对本发明的上述内容做进一步详细说明，但不应该将此理解为本发明上述主题的范围仅限于以下的实施例，凡基于本发明上述内容实现的技术均属于本发明的范围。
实施例1
分别称取0.008mol的氢氧化锂和0.004mol的硫代钼酸铵，在玛瑙研钵中混合研磨1h，将研磨后的混合物置于刚玉坩埚中，放置在管式炉中，通氩气保护，程序升温至400℃，保温1h，然后继续通氩气自然降温至室温，得到插锂的2H相硫化钼（Li2MoS4）块体；将插锂的硫化钼块体置于盛有100mL去离子水的容器中，超声分散10min，分散后的悬浮液在转速为1000r/min的离心机上离心分离沉淀；根据去除沉淀后悬浮液中的二硫化钼含量加入1:0.1质量比的导电碳黑（乙炔黑）得到混合悬浮液，在90mL混合悬浮液中加入2g十六烷基三甲基溴化铵，超声分散30min后，得到单层2H相MoS2/碳黑悬浮液；将得到的单层2H相MoS2/碳黑悬浮液在转速为4000r/min的离心机上分别用水和乙醇离心洗涤3次去除可溶性杂质，最后将沉淀物单层2H相二硫化钼/碳黑复合材料分散于200mL去离子水中保存。所得的单层2H相二硫化钼/碳黑复合材料中碳含量约为10%。
实施例2
分别称取0.008mol的醋酸锂和0.004mol的硫代钼酸铵，在玛瑙研钵中混合研磨1h，将研磨后的混合物置于刚玉坩埚中，放置在管式炉中，通氩气保护，程序升温至200℃，保温10h，然后继续通氩气自然降温至室温，得到插锂的2H相硫化钼（Li2MoS4）块体；将插锂的硫化钼块体置于盛有200mL去离子水的容器中，超声分散10min，分散后的悬浮液在转速为1000r/min的离心机上离心分离沉淀；根据去除沉淀后悬浮液中的二硫化钼含量加入1:0.01质量比的碳纳米管得到混合悬浮液，在190mL混合悬浮液中加入2g十六烷基三甲基溴化铵，超声分散20min后，得到单层2H相MoS2/碳纳米管悬浮液；将得到的单层2H相MoS2/碳纳米管悬浮液在转速为10000r/min的离心机上分别用水和乙醇离心洗涤3次去除可溶性杂质，最后将沉淀物单层2H相二硫化钼/碳纳米管复合材料分散于200mL无水乙醇中保存。所得的单层2H相二硫化钼/碳纳米管复合材料中碳含量约为1.0%。
实施例3
分别称取0.008mol的硝酸锂和0.004mol的硫代钼酸铵，在玛瑙研钵中混合研磨1h，将研磨后的混合物置于刚玉坩埚中，放置在管式炉中，通氩气保护，程序升温至300℃，保温5h，然后继续通氩气自然降温至室温，得到插锂的2H相硫化钼（Li2MoS4）块体；将插锂的硫化钼块体置于盛有100mL去离子水的容器中，超声分散5min，分散后的悬浮液在转速为1000r/min的离心机上离心分离沉淀；根据去除沉淀后悬浮液中的二硫化钼含量加入1:0.005质量比的还原氧化石墨烯得到混合悬浮液，在90mL混合悬浮液中加入0.5g十六烷基三甲基溴化铵，超声分散10min，得到单层2H相MoS2/还原氧化石墨烯悬浮液；将得到的单层2H相MoS2/还原氧化石墨烯悬浮液在转速为20000r/min的离心机上分别用水和乙醇离心洗涤3次去除可溶性杂质，最后将沉淀物单层2H相二硫化钼/还原氧化石墨烯复合材料分散于200mL异丙醇中保存。所得的单层2H相二硫化钼/还原氧化石墨烯复合材料中碳含量约为0.5%。
实施例4
分别称取0.008mol的碳酸锂和0.004mol的硫代钼酸铵，在玛瑙研钵中混合研磨1h，研磨后的将混合物置于刚玉坩埚中，放置在管式炉中，通氩气保护，程序升温至300℃，保温5h，然后继续通氩气自然降温至室温，得到插锂的2H相硫化钼（Li2MoS4）块体；将插锂的硫化钼块体置于盛有100mL去离子水的容器中，超声分散30min，分散后的悬浮液在转速为1000r/min的离心机上离心分离沉淀；根据去除沉淀后悬浮液中的二硫化钼含量加入1:0.2质量比的纳米碳纤维得到混合悬浮液，在90mL混合悬浮液中加入4g十六烷基三甲基溴化铵，超声分散20min，得到单层2H相MoS2/纳米碳纤维悬浮液；将得到的单层2H相MoS2/纳米碳纤维悬浮液在转速为8000r/min的离心机上分别用水和乙醇离心洗涤3次去除可溶性杂质，最后将沉淀物单层2H相二硫化钼/纳米碳纤维复合材料分散于200mL N-甲基吡咯烷酮中保存。所得的单层2H相二硫化钼/纳米碳纤维复合材料中碳的含量约为20%。
以上实施例描述了本发明的基本原理、主要特征及优点，本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明原理的范围下，本发明还会有各种变化和改进，这些变化和改进均落入本发明保护的范围内。
Claims (6)
1.一种制备单层2H相二硫化钼/微纳米碳复合材料的方法，其特征在于具体步骤为：
（1）将硫代钼酸铵和锂盐化合物按1:2摩尔比混合研磨，研磨后的混合物在惰性气体保护下于200-400℃保温1-10h，冷却至室温得到插锂的2H相硫化钼块体；
（2）将插锂的2H相硫化钼块体直接置于去离子水中，辅助超声水解剥离5-30min，再将得到的悬浮液置于离心机中，经离心分离去除未剥离的沉淀物后得到单层2H相MoS2纳米片悬浮液；
（3）将微纳米碳加入到单层2H相MoS2纳米片悬浮液中得到混合悬浮液，再加入十六烷基三甲基溴化铵，其中十六烷基三甲基溴化铵的质量与混合悬浮液的体积比为1g:22.5-180mL，然后超声分散10-30min得到单层2H相MoS2/微纳米碳悬浮液；
（4）将得到的单层2H相MoS2/微纳米碳悬浮液在离心机上分别用水和乙醇离心洗涤去除可溶性杂质，最后将沉淀物单层2H相二硫化钼/微纳米碳复合材料分散于小分子溶剂中保存，其中单层2H相MoS2纳米片的厚度小于1nm。
2.根据权利要求1所述的制备单层2H相二硫化钼/微纳米碳复合材料的方法，其特征在于：步骤（1）中所述的锂盐化合物为氯化锂、醋酸锂、碳酸锂、硫酸锂或硝酸锂中的一种或多种。
3.根据权利要求1所述的制备单层2H相二硫化钼/微纳米碳复合材料的方法，其特征在于：步骤（3）中所述的微纳米碳为导电碳黑、纳米碳纤维、碳纳米管、石墨粉或还原氧化石墨烯。
4.根据权利要求1所述的制备单层2H相二硫化钼/微纳米碳复合材料的方法，其特征在于：步骤（2）中所述的离心机转速为1000r/min，步骤（4）中所述的离心机转速为4000-20000r/min。
5.根据权利要求1所述的制备单层2H相二硫化钼/微纳米碳复合材料的方法，其特征在于：步骤（3）中所述的微纳米碳与单层2H相MoS2纳米片悬浮液中MoS2的质量比为0.005-0.2:1。
6.根据权利要求1所述的制备单层2H相二硫化钼/微纳米碳复合材料的方法，其特征在于：步骤（4）中所述的小分子溶剂为水、甲醇、乙醇、异丙醇、丁醇、丙酮、N-甲基吡咯烷酮或N-甲基甲酰胺。
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