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CN107331844A - 一种网络多孔氮掺杂石墨烯纳米片的制备方法 - Google Patents

一种网络多孔氮掺杂石墨烯纳米片的制备方法 Download PDF

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CN107331844A
CN107331844A CN201710529298.9A CN201710529298A CN107331844A CN 107331844 A CN107331844 A CN 107331844A CN 201710529298 A CN201710529298 A CN 201710529298A CN 107331844 A CN107331844 A CN 107331844A
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阎兴斌
杨兵军
陈江涛
程斌斌
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Lanzhou Institute of Chemical Physics LICP of CAS
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Abstract

本发明公开了一种网络多孔氮掺杂石墨烯纳米片的制备方法。本发明通过含氮有机物和水溶性盐模板混合，直接惰性气氛下高温梯度煅烧制备网络多孔氮掺杂石墨烯纳米片。制备的网络多孔氮掺杂石墨烯纳米片作为钠/钾电池负极材料，具有优异的性能。

Description

一种网络多孔氮掺杂石墨烯纳米片的制备方法
技术领域
本发明涉及一种网络多孔氮掺杂石墨烯纳米片的制备方法。
背景技术
石墨烯是一类碳原子构成的正六边形扩展的二维网格结构的纳米材料，由于其性能优异且具有多种潜在的应用。收到人们的广泛关注。然而，二维石墨烯之间又极易层-层相互叠加使其丧失二维纳米结构的特有性质，因此，如何阻止石墨烯分子层-层之间的叠加，使其在宏观尺度依旧保持其石墨烯特性成为科学研究需要解决的关键问题。
因此，通过三维网络石墨烯构筑，从而在宏观尺度保持石墨烯的二维特性成为当今纳米材料领域的研究热点(Nat Mater, 2011, 10: 424； Adv Mater, 2012, 24: 5083；CN201611191949.X；CN201611232796.9)。相关研究表明，异质原子掺杂可以氮掺杂改变石墨烯分子上的电子云密度，因而具有独特的材料特性，氮原子掺杂的石墨烯由于石墨烯分子内C-N键间的极性，致使氮掺杂石墨烯催化氧还原性能优于石墨烯。三维氮掺杂石墨烯的制备方法通常通过三维石墨烯在氨气气氛还原得到（ACS Nano, 2013, 7(5): 4042），这种方法工艺繁琐，同时氨气的使用有一定的危险性，因而开发一种简单规模制备网络氮掺杂石墨烯纳米片的方法非常必要。
发明内容
针对上述现有技术存在的问题，本发明的目的是提出一种网络多孔氮掺杂石墨烯纳米片的制备方法。
本发明通过含氮有机物和水溶性盐模板混合，直接惰性气氛下高温梯度煅烧制备网络多孔氮掺杂石墨烯纳米片。
一种网络多孔氮掺杂石墨烯纳米片的制备方法，其特征在于将含氮有机物与可水溶性盐模板混合，然后置入气氛炉中梯度煅烧：首先按照升温速度1-10 ℃/min，升温至300-500 ℃，保温0.5-2h后，继续升温至600-1500 ℃，升温速度1-10 ℃/min，保温时间为1-3 h，降至室温后取出；煅烧后成黑色块状，粉碎后，每次加入原料质量的2-5倍30-100 ℃蒸馏水抽滤洗涤，将滤渣60-120 ℃恒温12-24 h烘干，得到网络多孔氮掺杂石墨烯纳米片。
本发明所述的含氮有机物选自柠檬酸三胺、乙二胺四乙酸或乙二酸二乙胺。
水溶性盐模板选自碳酸氢钠或碳酸氢钾。
含氮有机物与水溶性盐模板的质量比为1:0.1-10。
本发明原材料丰富、廉价易得、设备要求简单、环境友好、产品质量稳定。其中通过将含氮有机物和水溶性盐模板混合后直接惰性气氛下高温梯度煅烧，通过粉碎、洗涤、烘干等到网络多孔氮掺杂石墨烯纳米片。
制备的网络多孔氮掺杂石墨烯纳米片作为钠/钾电池负极材料，具有优异的性能。
本发明与其他网络状石墨烯纳米片制备方法相比，具有以下优点：
1、本方法原料廉价易得，制备所用原料均为含氮有机物和水溶性盐，产地广泛且价格低廉；
2、本方法无需高真空设备，设备要求简单；
3、本方法环境相对友好，不涉及易燃气体，产生废水中所含大部分为无机盐类，易于回收，环境污染小；
4、所制备材料作为钠/钾电池负极，具有优异的性能，同时可广泛用于储能，光催化，高分子填料等领域。
附图说明
图1为实施例1中所制备网络多孔氮掺杂石墨烯纳米片TEM照片。
图2为实施例3中所制备网络多孔氮掺杂石墨烯纳米片TEM照片。
图3为实施例1中所制备网络多孔氮掺杂石墨烯纳米片氮含量EDX谱图。
图4为实施例1中所制备网络多孔氮掺杂石墨烯纳米片钾离子半电池测试。
具体实施方式
实施例1：
称取10 g 柠檬酸三胺和30 g碳酸氢钠球磨混合均匀后加入瓷舟中，置入氩气气氛炉中，首先，按照升温速率5 ℃/min升温至400 ℃，保温2 h后，继续按照5 ℃/min升温至800℃，保温1 h后，自然降至室温，取出样品；将所得黑色块状样品粉碎后，加入50 ℃蒸馏水80g进行抽滤洗涤，反复进行5次，将洗涤后的滤渣60 ℃ 保温12 h干燥得到网络多孔氮掺杂石墨烯纳米片。
实施例2：
称取10 g 柠檬酸三胺和100 g碳酸氢钾球磨混合均匀后加入瓷舟中，置入氩气气氛炉中，首先，按照升温速率2 ℃/min升温至500 ℃，保温0.5 h后，继续按照10 ℃/min升温至1500 ℃，保温1 h后，自然降至室温，取出样品；将所得黑色块状样品粉碎后，加入100 ℃蒸馏水500 g进行抽滤洗涤，反复进行3次，将洗涤后的滤渣80 ℃ 保温24 h干燥得到网络多孔氮掺杂石墨烯纳米片。
实施例3：
称取10 g 乙二酸二乙胺和5 g碳酸氢钠机械混合均匀后加入瓷舟中，置入氮气气氛炉中，首先，按照升温速率10 ℃/min升温至400 ℃，保温2 h后，继续按照5 ℃/min升温至800℃，保温2 h后，自然降至室温，取出样品；将所得黑色块状样品粉碎后，加入80 ℃蒸馏水45g进行抽滤洗涤，反复进行8次，将洗涤后的滤渣80 ℃ 保温24 h干燥得到网络多孔氮掺杂石墨烯纳米片。
实施例4：
称取10 g 乙二酸二乙胺和10 g碳酸氢钾机械混合均匀后加入瓷舟中，置入氮气气氛炉中，首先，按照升温速率5 ℃/min升温至300 ℃，保温1 h后，继续按照5 ℃/min升温至900 ℃，保温1 h后，自然降至室温，取出样品；将所得黑色块状样品粉碎后，加入80 ℃蒸馏水50 g进行抽滤洗涤，反复进行5次，将洗涤后的滤渣120 ℃ 保温20 h干燥得到网络多孔氮掺杂石墨烯纳米片。
实施例5：
称取10 g乙二胺四乙酸和40 g碳酸氢钾机械混合均匀后加入瓷舟中，置入氮气气氛炉中，首先，按照升温速率5 ℃/min升温至500 ℃，保温1 h后，继续按照5 ℃/min升温至900℃，保温1 h后，自然降至室温，取出样品；将所得黑色块状样品粉碎后，加入80 ℃蒸馏水50g进行抽滤洗涤，反复进行5次，将洗涤后的滤渣80 ℃ 保温20 h干燥得到网络多孔氮掺杂石墨烯纳米片。
实施例6：
称取10 g乙二胺四乙酸和20 g碳酸氢钠机械混合均匀后加入瓷舟中，置入氮气气氛炉中，首先，按照升温速率5 ℃/min升温至300 ℃，保温1.5 h后，继续按照5 ℃/min升温至900 ℃，保温1 h后，自然降至室温，取出样品；将所得黑色块状样品粉碎后，加入80 ℃蒸馏水50 g进行抽滤洗涤，反复进行5次，将洗涤后的滤渣80 ℃ 保温14 h干燥得到网络多孔氮掺杂石墨烯纳米片。
实施例7：
称取10 g 乙二酸二乙胺和50 g碳酸氢钾机械混合均匀后加入瓷舟中，置入氮气气氛炉中，首先，按照升温速率5 ℃/min升温至300 ℃，保温1.5 h后，继续按照5 ℃/min升温至900 ℃，保温1 h后，自然降至室温，取出样品；将所得黑色块状样品粉碎后，加入80 ℃蒸馏水50 g进行抽滤洗涤，反复进行5次，将洗涤后的滤渣80 ℃ 保温14 h干燥得到网络多孔氮掺杂石墨烯纳米片。
实施例8：
称取10 g 柠檬酸三胺和2 g碳酸氢钾机械混合均匀后加入瓷舟中，置入氮气气氛炉中，首先，按照升温速率5 ℃/min升温至300 ℃，保温1.5 h后，继续按照5 ℃/min升温至900 ℃，保温1 h后，自然降至室温，取出样品；将所得黑色块状样品粉碎后，加入80 ℃蒸馏水30 g进行抽滤洗涤，反复进行5次，将洗涤后的滤渣80 ℃ 保温14 h干燥得到网络多孔氮掺杂石墨烯纳米片。
试验例1
本试验例将各实施例所得网络状石墨烯纳米片作为钠离子电池电极材料组装钠离子半电池：选择钠片为对电极，0.8 M KPF6溶于EC/DMC(1：1 体积比) 作为电解液，在手套箱（水含量小于0.1 ppm，氧含量小于0.3 ppm）里进行CR2032半电池组装后测试。测试电流密度为0.1A/g，检测结果表1所示，实施例1的钾电性能如图4所示。
表1各实施例的网络多孔氮掺杂石墨烯纳米片0.1A g-1的钾电性能检测结果
。

Claims (4)

1.一种网络多孔氮掺杂石墨烯纳米片的制备方法，其特征在于将含氮有机物与可水溶性盐模板混合，然后置入气氛炉中梯度煅烧：首先按照升温速度1-10 ℃/min，升温至300-500 ℃，保温0.5-2h后，继续升温至600-1500 ℃，升温速度1-10 ℃/min，保温时间为1-3h，降至室温后取出；煅烧后成黑色块状，粉碎后，每次加入原料质量的2-5倍30-100 ℃蒸馏水抽滤洗涤，将滤渣60-120 ℃恒温12-24 h烘干，得到网络多孔氮掺杂石墨烯纳米片。
2.根据权利要求1中所述的制备方法，其特征在于含氮有机物选自柠檬酸三胺、乙二胺四乙酸或乙二酸二乙胺。
3.根据权利要求1中所述的制备方法，其特征在于水溶性盐模板选自碳酸氢钠或碳酸氢钾
4.根据权利要求1或2或3中所述的制备方法，其特征在于含氮有机物与水溶性盐模板的质量比为1:0.1-10。
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CN108735991A (zh) * 2018-05-07 2018-11-02 北京科技大学 一种钾离子电池用负极材料及制备方法和电解液
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Cited By (4)

* Cited by examiner, † Cited by third party
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CN108232116A (zh) * 2017-12-15 2018-06-29 江苏大学 一种氮、磷共掺杂石墨烯凝胶电化学储钠电极的制备方法
CN108735991A (zh) * 2018-05-07 2018-11-02 北京科技大学 一种钾离子电池用负极材料及制备方法和电解液
CN108735991B (zh) * 2018-05-07 2021-03-05 北京科技大学 一种钾离子电池用负极材料及制备方法和电解液
CN109286018A (zh) * 2018-12-06 2019-01-29 中国科学院兰州化学物理研究所 一种超薄二维碳片的制备方法

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