CN110265225B - 制备氮掺杂三维多孔碳微球负载碳化钼/氮化钼和铁纳米颗粒复合材料的方法 - Google Patents
制备氮掺杂三维多孔碳微球负载碳化钼/氮化钼和铁纳米颗粒复合材料的方法 Download PDFInfo
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Abstract
本发明提供一种制备氮掺杂三维多孔碳微球负载碳化钼/氮化钼和铁纳米颗粒复合材料的方法，包括以下步骤：1)制备前驱体：选用氯化铁、七钼酸铵、柠檬酸铵和氯化钠为原料，将以上原料混合溶解在去离子水中，将所得的均一混合溶液利用喷雾干燥机喷雾成球，从而制得前驱体；2)制备氮掺杂三维多孔碳微球负载碳化钼/氮化钼和铁纳米颗粒复合材料：将步骤1制得的前驱体在管式炉中煅烧，再冷却至室温，得到煅烧产物，去除NaCl得到氮掺杂三维多孔碳微球负载碳化钼/氮化钼和铁纳米颗粒复合材料。
Description
技术领域
本发明涉及一种使用工业化生产技术(喷雾干燥法)制备氮掺杂三维多孔碳微球负载碳化钼/氮化钼和铁纳米颗粒的方法，属于纳米材料制备技术领域。
背景技术
氮掺杂的三维多孔碳微球具有着优异的理化性质，例如：大的比表面积、高的机械强度、优良的导电性和导热性等，因而其可以应用在诸多领域，特别是在电化学领域，丰富的孔结构和掺杂的氮原子使得该多孔碳微球可被作为负载基体负载多种纳米金属颗粒或金属基纳米材料，制备的该种复合材料可作为高性能电极材料应用在多种领域，譬如：钠离子电池及锂离子电池正负极材料、超电容、锂-硫电池、锂金属电池以及电催化析氢和吸氧等。
当前，水热、溶剂热结合模板技术是制备多孔球形碳负载金属及其化合物的主流方法。但水热和溶剂热结合模板技术生产成本较高，过程较为复杂，产量较低，不适合大规模工业化生产制备。同时，将多种金属基材料共同负载在氮掺杂的多孔碳微球上更是很难实现。这些都严重限制了其在电化学领域的实际应用和性能的提高。所以大批量和高纯度的制备氮掺杂三维多孔碳微球负载碳化钼/氮化钼和铁纳米颗粒同样依然是一个难题。
发明内容
本发明的目的是提供一种简易制备氮掺杂三维多孔碳微球负载碳化钼/氮化钼和铁纳米颗粒的方法；该方法过程简单，成本低廉，得到的氮掺杂三维多孔碳微球负载碳化钼/氮化钼和铁纳米颗粒复合材料形貌均匀一致、产量大，适合大规模工业化生产。本发明解决上述技术问题的技术方案是，
一种制备氮掺杂三维多孔碳微球负载碳化钼/氮化钼和铁纳米颗粒复合材料的方法，包括以下步骤：
1)制备前驱体
选用氯化铁(FeCl3)、七钼酸铵((NH4)6Mo7O24·4H2O)、柠檬酸铵(C6H5O7(NH4)3)和氯化钠(NaCl)为原料，将以上原料混合溶解在去离子水中，将所得的均一混合溶液利用喷雾干燥机喷雾成球，从而制得前驱体，记为NaCl@FeCl3-C6H5O7(NH4)3-(NH4)6Mo7O24·4H2O。
2)制备氮掺杂三维多孔碳微球负载碳化钼/氮化钼和铁纳米颗粒复合材料
将步骤1制得的前驱体在管式炉中高纯氩气气氛下以8℃/min升温至780～790℃，保温大于等于2h，再冷却至室温，得到煅烧产物，记为Fe/Mo2C/Mo2N@N-3DC@NaCl，再将Fe/Mo2C/Mo2N@N-3DC@NaCl去除NaCl得到Fe/Mo2C/Mo2N@N-3DC，即得到氮掺杂三维多孔碳微球负载碳化钼/氮化钼和铁纳米颗粒复合材料。
步骤1)中，按照Fe3+:Mo:C:Na+的物质量之比为(0.2-0.5):(2-3):(25-35):100的关系，将原料混合溶解在去离子水中。
与现有技术相比，本发明方法具有以下优势：(1)利用NaCl(可回收再利用)作为模板，使用廉价的FeCl3、C6H5O7(NH4)3和(NH4)6Mo7O24·4H2O作为原料，大大节约了成本；(2)所制备的氮掺杂三维多孔碳微球负载碳化钼/氮化钼和铁纳米颗粒复合材料纯度高，产量大，可控性好，且制备过程和设备简单，易于未来大规模工业化实际生产应用。
附图说明
图1为本发明制备的经水洗去除NaCl后Fe/Mo2C/Mo2N@N-3DC的XRD图谱；
图2为本发明制备的前驱体NaCl@FeCl3-C6H5O7(NH4)3-(NH4)6Mo7O24·4H2O的SEM图像；
图3为本发明所制备的煅烧产物Fe/Mo2C/Mo2N@N-3DC@NaCl的SEM图像；
图4为本发明所制备的经水洗去除NaCl后Fe/Mo2C/Mo2N@N-3DC的SEM图像；
图5为本发明所制备的经水洗去除NaCl后Fe/Mo2C/Mo2N@N-3DC(为Mo2C)的TEM图像。
图6为本发明所制备的经水洗去除NaCl后Fe/Mo2C/Mo2N@N-3DC(为Mo2N)的TEM图像。
图7为本发明所制备的经水洗去除NaCl后Fe/Mo2C/Mo2N@N-3DC(为Fe)的TEM图像。
图8为本发明所制备的经水洗去除NaCl后Fe/Mo2C/Mo2N@N-3DC(为Fe)的HRTEM图像。
本发明未述及之处适用于现有技术。
以下给出本发明制备方法的具体实施例。这些实施例仅用于详细说明本发明制备方法，并不限制本申请权利要求的保护范围。
实施例1
按照Fe3+:Mo:C:Na+的物质量之比为0.5:2:30:100的关系，将0.19g的FeCl3，2.9g的C6H5O7(NH4)3，0.842g的(NH4)6Mo7O24·4H2O和15g的NaCl溶于115mL去离子水，在室温下搅拌8h以保证C6H5O7(NH4)3与金属盐充分络合。将所得均一溶液通过喷雾干燥机进行喷雾干燥。在此过程中，被包袱着(NH4)6Mo7O24.4H2O、C6H5O7(NH4)3和FeCl3的NaCl自组装形成空心圆球，圆球的大小成正态分布。由于在高温下，液滴表面的水迅速挥发，液滴内部的水携带着NaCl迁移至表面，在极短的时间内导致其自组装形成空心圆球前驱体NaCl@FeCl3-C6H5O7(NH4)3-(NH4)6Mo7O24·4H2O。将前驱体置于管式炉中，先通氩气以排除空气，然后以8℃/min升温至790℃，保温2h，后冷却至室温，得到煅烧产物Fe/Mo2C/Mo2N@N-3DC@NaCl。将产物用去离子水和无水乙醇洗涤三次，烘干得到样品Fe/Mo2C/Mo2N@N-3DC。
实施例2
按照Fe3+:Mo:C:Na+的物质量之比为0.25:2.5:30:100的关系，将0.097g的FeCl3，2.9g的C6H5O7(NH4)3，1.053g的(NH4)6Mo7O24·4H2O和15g的NaCl溶于115mL去离子水，在室温下搅拌12h以保证C6H5O7(NH4)3与金属盐充分络合。将所得均一溶液通过喷雾干燥机进行喷雾干燥。在此过程中，被包袱着(NH4)6Mo7O24.4H2O、C6H5O7(NH4)3和FeCl3的NaCl自组装形成空心圆球，圆球的大小成正态分布。由于在高温下，液滴表面的水迅速挥发，液滴内部的水携带着NaCl迁移至表面，在极短的时间内导致其自组装形成空心圆球前驱体NaCl@FeCl3-C6H5O7(NH4)3-(NH4)6Mo7O24·4H2O。将前驱体置于管式炉中，先通氩气以排除空气，然后以8℃/min升温至780℃，保温3h，后冷却至室温，得到煅烧产物Fe/Mo2C/Mo2N@N-3DC@NaCl。将产物用去离子水和无水乙醇洗涤三次，烘干得到样品Fe/Mo2C/Mo2N@N-3DC。
实施例3
按照Fe3+:Mo:C:Na+的物质量之比为0.21:1.4:21:100的关系，将0.116g的FeCl3，2.9g的C6H5O7(NH4)3，0.842g的(NH4)6Mo7O24·4H2O和20g的NaCl溶于115mL去离子水，在室温下搅拌6h以保证C6H5O7(NH4)3与金属盐充分络合。将所得均一溶液通过喷雾干燥机进行喷雾干燥。在此过程中，被包袱着(NH4)6Mo7O24.4H2O、C6H5O7(NH4)3和FeCl3的NaCl自组装形成空心圆球，圆球的大小成正态分布。由于在高温下，液滴表面的水迅速挥发，液滴内部的水携带着NaCl迁移至表面，在极短的时间内导致其自组装形成空心圆球前驱体NaCl@FeCl3-C6H5O7(NH4)3-(NH4)6Mo7O24·4H2O。将前驱体置于管式炉中，先通氩气以排除空气，然后以8℃/min升温至785℃，保温2.5h，后冷却至室温，得到煅烧产物Fe/Mo2C/Mo2N@N-3DC@NaCl。将产物用去离子水和无水乙醇洗涤三次，烘干得到样品Fe/Mo2C/Mo2N@N-3DC。
Claims (3)
1.一种制备氮掺杂三维多孔碳微球负载碳化钼/氮化钼和铁纳米颗粒复合材料的方法，包括以下步骤：
1） 制备前驱体
选用氯化铁FeCl3、七钼酸铵(NH4)6Mo7O24·4H2O、柠檬酸铵C6H5O7(NH4)3和氯化钠NaCl为原料，将以上原料混合溶解在去离子水中，将所得的均一混合溶液利用喷雾干燥机喷雾成球，从而制得前驱体，记为NaCl@FeCl3-C6H5O7(NH4)3-(NH4)6Mo7O24·4H2O；
2） 制备氮掺杂三维多孔碳微球负载碳化钼/氮化钼和铁纳米颗粒复合材料
将步骤1）制得的前驱体在管式炉中在惰性气氛下升温至780~790℃，保温大于等于2h，再冷却至室温，得到煅烧产物，记为Fe/Mo2C/Mo2N@N-3DC@NaCl，再将Fe/Mo2C/Mo2N@N-3DC@NaCl去除NaCl得到Fe/Mo2C/Mo2N@N-3DC，即得到氮掺杂三维多孔碳微球负载碳化钼/氮化钼和铁纳米颗粒复合材料。
2.根据权利要求1所述的方法，其特征在于，步骤1）中，按照Fe3+:Mo:C:Na+的物质量之比为（0.2-0.5）:（2-3）:（25-35）:100的关系，将原料混合溶解在去离子水中。
3.根据权利要求1所述的方法，其特征在于，步骤2）中，在管式炉中高纯氩气气氛下以8℃/min升温至780~790℃。
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