CN106960953A - 一种氮掺杂碳纤维材料的制备方法 - Google Patents

一种氮掺杂碳纤维材料的制备方法 Download PDF

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CN106960953A
CN106960953A CN201710279692.1A CN201710279692A CN106960953A CN 106960953 A CN106960953 A CN 106960953A CN 201710279692 A CN201710279692 A CN 201710279692A CN 106960953 A CN106960953 A CN 106960953A
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nitrogen
carbon fiber
ammonium
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侯朝辉
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Hunan Institute of Science and Technology
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Abstract

本发明属于碳纤维材料技术领域，具体为采用低温热解法对碳纤维进行氮原子掺杂。该方法采用廉价的氮源和碳纤维为原料，控制氮源与碳纤维的质量比为1：（1～10），采用低温热解法制备氮掺杂的碳纤维。本发明所述工艺方法的原料廉价易得、工艺简单、成本较低，适合扩大生产，对锂离子电池负极材料储锂性能的改善有重要现实意义，因而本发明具有潜在的推广应用价值。

Description

一种氮掺杂碳纤维材料的制备方法
技术领域
本发明属于碳纤维材料技术领域，具体为采用低温热解法对碳纤维进行氮原子掺杂。
背景技术
随着各种电子产品的出现，使电化学能量储存与转化技术越来越受到世界各国的重视。锂离子电池（LIBs）具有能量密度高、循环寿命长、自放电率小以及无污染等优点，已在移动设备、数字电子器件等领域获得了广泛应用。目前，商业化LIBs通常以石墨化碳作为负极材料，其理论比容量为372 mAh/g，所提供的能量密度约150Wh/kg，已不能满足对混合电动汽车、纯电动汽车的需求。因此，开发新型高比容量负极材料是发展下一代锂离子电池的关键之一。
氮掺杂碳纤维作为LIBs负极材料，具有电导率高、比容量高、循环性能稳定等优势，被认为是一种较为理想的电极材料。Qie等[1]研究发现掺氮碳纤维的可逆比容量高达943 mAh g−1，Wang等[2]研究发现掺氮碳纤维在电流密度0.1 A g−1下循环400圈之后比容量保留83.7% 。目前，常用的制备氮掺杂碳纤维的方法有化学气相沉积法[3]、原位生长法[4]，其多数需要较高的温度，工艺条件苛刻，不能大量制备。因此，使用廉价的氮源和碳源，开发合成工艺简单且易于大量制备杂原子掺杂的碳材料受到了各个领域的密切关注。
综上，本发明采用一种较温和、操作简单、成本低廉、易于扩大的化学工艺，制备了氮掺杂碳纤维材料。本发明旨在提供一种比容量高、循环性能和倍率性能优异的LIBs负极材料制备方法。
参考文献。
[1] Qie L, Chen W M, Wang Z H, et al. Nitrogen‐doped porous carbonnanofiber webs as anodes for lithium ion batteries with a superhigh capacityand rate capability[J]. Advanced materials, 2012, 24(15): 2047-2050。
[2] Wang H, Yuan C, Zhou R, et al. Self-sacrifice template formationof nitrogen-doped porous carbon microtubes towards high performance anodematerials in lithium ion batteries[J]. Chemical Engineering Journal, 2017,316: 1004-1010。
[3] Qu L, Liu Y, Baek J B, et al. Nitrogen-doped graphene asefficient metal-free electrocatalyst for oxygen reduction in fuel cells[J].ACS nano, 2010, 4(3): 1321-1326。
[4] Tian G L, Zhao M Q, Yu D, et al. Nitrogen‐Doped Graphene/CarbonNanotube Hybrids: In Situ Formation on Bifunctional Catalysts and TheirSuperior Electrocatalytic Activity for Oxygen Evolution/Reduction Reaction[J]. Small, 2014, 10(11): 2251-2259。
发明内容
本发明旨在提供一种氮掺杂碳纤维的制备方法，并将其应用于锂离子电池储能领域。
本发明提供了一种氮掺杂碳纤维材料的低温制备方法，并测试材料的储锂性能，具体方法如下：
（1）将氮源（尿素、碳酸铵、碳酸氢铵、氯化铵、硫酸铵、硝酸铵、三聚氰胺、磷酸二氢铵和磷酸氢二铵）和碳纤维以质量比为1:（1～10）分开放入水热反应釜中，密封。
（2）在180~200℃条件下，反应5~24小时，结束后冷却至室温，得到最终产物氮掺杂碳纤维材料。
（3）将所得的氮掺杂碳纤维材料作为锂离子电池负极，测试其储锂性能。
本发明所述工艺方法的原料廉价易得、工艺简单、成本较低，适合扩大生产，对LIBs负极材料储锂性能的改善有重要现实意义，因而本发明具有潜在的推广应用价值。
附图说明
附图1为本发明实施例1所得氮掺杂碳材料和碳纤维的X射线衍射分析图。
附图2为本发明实施例1所得氮掺杂碳材料的扫描电子显微镜照片。其中，图（a）是低倍率透射电子显微镜照片，图（b）是高倍率透射电子显微镜照片。
附图3为本发明实施例2所得氮掺杂碳材料和碳纤维的X射线光电子能谱图。
附图4为本发明实施例3所得氮掺杂碳材料的透射电子显微镜照片。其中，图（a）是低倍率透射电子显微镜照片，图（b）是高倍率透射电子显微镜照片。
附图5为本发明实施例3所得氮掺杂碳材料的循环性能测试曲线；
附图6为本发明实施例4所得氮掺杂碳材料的倍率性能测试曲线。
具体实施方式
下列实施例中所使用的方法如无特殊说明，均为常规方法。
下列实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
实施例1
将尿素和碳纤维以质量比为1:5分开放入水热反应釜中，密封后，在180℃条件下，水热反应12小时，反应结束后冷却至室温，得到最终产物氮掺杂碳纤维材料。
实施例1所得材料用X射线衍射来分析晶体结构，如图1所示，结果表明实施例1制备的碳纤维主要由无定型碳组成。
采用扫描电子显微镜检测实施例1得到的氮掺杂碳纤维材料的形貌，如图2所示，结果表明实施例1制备的氮掺杂碳纤维形貌为纤维状。
实施例2
将碳酸铵和碳纤维以质量比为1:8分开放入水热反应釜中，密封后，在200℃条件下，水热反应12小时，反应结束后冷却至室温，得到最终产物氮掺杂碳纤维材料。
实施例2所得材料用能谱仪来分析所含元素，结果如图3所示，证明了氮元素对碳纤维进行了掺杂。
实施例3
将碳酸铵和碳纤维以质量比为1:10分开放入水热反应釜中，密封后，在180℃条件下，水热反应15小时，反应结束后冷却至室温，得到最终产物氮掺杂碳纤维材料。
采用电子透射电镜检测实施例3得到的氮掺杂碳纤维材料的形貌，如图4所示，结果表明实施例3制备的氮掺杂碳纤维形貌为纤维状。
实施例3所得材料组装成扣式电池，采用蓝电电池测试系统来测试电池的循环性能。如图5所示，结果表明实施例3制备的氮掺杂碳纤维材料具有优异的循环性能，在电流密度1A/g下循环500次后，比容量仍保留400 mAh/g。
实施例4
将磷酸二氢铵和碳纤维以质量比为1:8分开放入水热反应釜中，密封后，在200℃条件下，水热反应12小时，反应结束后冷却至室温，得到最终产物氮掺杂碳纤维材料。
实施例4所得材料组装成扣式电池，采用蓝电电池测试系统来测试电池的倍率性能。如图6所示，结果表明实施例4制备的氮掺杂碳纤维材料具有优异的倍率性能，经过电流密度20A/g循环后，电流密度又恢复到0.1A/g时，比容量恢复到最初值600 mAh/g。

Claims (4)

1.本发明提供了一种氮掺杂碳纤维材料的制备方法，具体步骤如下：
（1）将固态氮源和碳纤维按质量比1:（1～10），分开放入水热反应釜中；
（2）密封后，在180~200℃条件下，反应5~24小时，反应结束后冷却至室温，即可得到氮掺杂碳纤维材料。
2.如权利要求1所述的方法，其特征在于：步骤（1）中氮源为尿素、硫脲、碳酸铵、碳酸氢铵、氯化铵、硫酸铵、硝酸铵、三聚氰胺、磷酸二氢铵和磷酸氢二铵。
3.如权利要求1所述的方法，其特征在于：步骤（1）中，尿素与碳纤维的质量比为1:（1～10）。
4.如权利要求1所述的方法，其特征在于：步骤（2）中反应温度为180~200℃，反应时间为5~24小时。
CN201710279692.1A 2017-04-26 2017-04-26 一种氮掺杂碳纤维材料的制备方法 Pending CN106960953A (zh)

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CN110255697A (zh) * 2019-06-26 2019-09-20 合肥工业大学 一种氮掺杂碳材阳极的制备及其在催化湿式空气氧化中的应用
CN111203236A (zh) * 2020-01-15 2020-05-29 清创人和生态工程技术有限公司 一种二硫化钴/碳纤维复合材料的制备方法及其应用

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110255697A (zh) * 2019-06-26 2019-09-20 合肥工业大学 一种氮掺杂碳材阳极的制备及其在催化湿式空气氧化中的应用
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CN111203236A (zh) * 2020-01-15 2020-05-29 清创人和生态工程技术有限公司 一种二硫化钴/碳纤维复合材料的制备方法及其应用
CN111203236B (zh) * 2020-01-15 2023-04-18 清创人和生态工程技术有限公司 一种二硫化钴/碳纤维复合材料的制备方法及其应用

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