Tuning and understanding the supercapacitance of heteroatom-doped graphene

Tuning and understanding the supercapacitance of heteroatom-doped graphene
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调节和理解杂原子掺杂石墨烯的超级电容

DOI:
10.1016/j.ensm.2015.09.002
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发表时间:
2015-11
影响因子:
20.4
通讯作者:
Yunhui Huang
Yunhui Huang
中科院分区:
材料科学1区
文献类型:
--
作者:
Yingke Zhou;Xiao Xu;Bin Shan;Yanwei Wen;Tingting Jiang;Jiming Lu;Shaowei Zhang;David P. Wilkinson;Jiujun Zhang;Yunhui Huang

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碳纳米材料有望用于制造高性能超级电容器。然而,它们的比电容和能量密度仍然需要进一步改进,以用于许多重要和具有挑战性的应用。在这里,我们报告了在低温(200 °C)下通过热退火方法合成的杂原子掺杂石墨烯的上级电容性能,并且实现了在0.2 A g−1下629 F g− 1的显著增强的比电容,在140 W kg−1下43 Wh kg− 1的能量密度,以及10,000次的循环寿命。分析了其优异性能的机理,提出了掺杂与电容的关联模型,并通过第一性原理计算进行了验证。热退火温度在杂原子的掺杂配置中起着关键作用,因此显著影响石墨烯的电容性能。如果在低温下退火,则非石墨掺杂剂配置占主导地位,诱导大的法拉第赝电容;如果在高温下退火,则石墨掺杂剂配置占主导地位,产生相对较低的双电层电容。这些发现表明,石墨烯的超电容可以通过合理掺杂杂原子来有目的地调节,这可能为进一步设计和应用先进的石墨烯基材料用于电化学超级电容器开辟新的策略。
Carbon nanomaterials are promising for making high-performance supercapacitors. However, their specific capacitances and energy densities still need further improvement for many important and challenging applications. Here we report the superior capacitive performance of heteroatom-doped graphene synthesized by a thermal annealing method at low temperature (200 °C), and remarkably enhanced specific capacitance of 629 F g−1at 0.2 A g−1, energy density of 43 Wh kg−1at 140 W kg−1, and cycle life of 10,000 times are achieved. The mechanisms for the outstanding performance are analyzed, and a corresponding model connecting the dopant and capacitance is proposed and validated by the first-principle calculations. The thermal annealing temperature plays a critical role in the dopant configuration of heteroatom and hence significantly affects the capacitive properties of graphene. If annealing at low temperature, non-graphitic dopant configuration is dominant, inducing a large Faradaic pseudocapacitance; if annealing at high temperature, graphitic dopant configuration is dominant, giving rise to a relatively lower electrical double layer capacitance. These findings demonstrate that the supercapacitance of graphene can be purposely tuned by the rational doping of heteroatoms, which may open up new strategies for further design and application of advanced graphene-based materials for electrochemical supercapacitors.
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