三维筋撑石墨烯负载氧化锰的超级电容器

doi:10.11949/0438-1157.20200797

摘要/Abstract

摘要：

石墨烯基超级电容器，其功率密度较高，但能量密度受限。开发以三维石墨烯材料为载体的复合型赝电容多孔电极，是解决方案之一。本文采用铵盐辅助化学发泡法，制备了三维筋撑石墨烯泡沫体（SG）；以SG为载体，采用水热还原法在其表面生长二氧化锰（MnO₂）纳米棒阵列，从而构建了MnO₂/SG自支撑多孔材料。利用MnO₂/SG复合电极，组装了超级电容器，在0.5 A·g^-1的电流密度下，比电容达343.6 F·g^-1；经5000次循环，其容量保持率为83.8%；在500 W·kg^-1的功率密度下，其能量密度达11.93 W·h·kg^-1。因此，MnO₂/SG复合电极是一种性能优异的赝电容材料，在电化学储能领域有良好的应用前景。

关键词: 三维石墨烯, 筋撑石墨烯, 多孔介质, 电化学, 载体, 超级电容器

Abstract:

Graphene has shown superiority for advanced carbon electrodes in supercapacitors， characterized by high power density but limited energy density. Combining pseudocapacitive materials with graphene can alleviate the problem. This work synthesized the three-dimensional strutted graphene (SG) via the ammonium-salt-assisted sugar-blowing method, and the self-supporting MnO₂/SG porous monolith was then constructed via growing manganese oxide (MnO₂) nanorod array on the SG support in hydrothermal process. When tested in supercapacitor， the MnO₂/SG hybrid electrode achieved a high specific capacitance of 343.6 F·g^-1 at a current density of 0.5 A·g^-1， exhibiting excellent cycling stability with 83.8% capacitance retention after 5000 cycles. The symmetric supercapacitor further showed a high energy density of 11.93 W·h·kg^-1 at a power density of 500 W·kg^-1. The impressive result indicates a promising prospect of the excellent MnO₂/SG hybrid to be applied to electrochemical energy storage.

Key words: three-dimensional graphene, strutted graphene, porous media, electrochemistry, support, supercapacitor

中图分类号:

TQ 031.2

李鑫健,王保禄,高天,王旗,王学斌. 三维筋撑石墨烯负载氧化锰的超级电容器[J]. 化工学报, 2020, 71(11): 5025-5034.

Xinjian LI,Baolu WANG,Tian GAO,Qi WANG,Xuebin WANG. Three-dimensional strutted graphene loading manganese oxide for supercapacitor[J]. CIESC Journal, 2020, 71(11): 5025-5034.

图/表 10

图1 加热煅烧过程简图

Fig.1 Schematic of heating process

图2 MnO2/SG合成示意图

Fig.2 Schematic of fabrication of MnO2/SG hybrid

图3 SG的SEM图[(a)、(b)]；不同水热反应时长下获得的MnO2/SG产品的SEM图[(c)~(f)]

Fig.3 SEM images of SG[(a)，(b)]; SEM images of MnO2/SG samples obtained at different hydrothermal time[(c)—(f)]

图4 M/SG-4h产品的TEM和HRTEM图

Fig.4 TEM and HRTEM images of M/SG-4h

图5 M/SG-4h产品的EDS和XRD表征

Fig.5 EDS and XRD characterizations of M/SG-4h

图6 M/SG-4h样品XPS谱图

Fig.6 XPS characterization of M/SG-4h

图7 三电极体系中MnO2/SG的电化学性能

Fig.7 Electrochemical performance of MnO2/SG in three-electrode system

图8 基于MnO2/SG的对称型超级电容器的性能(SG的数据用于对比)

Fig.8 Performance of MnO2/SG symmetric supercapacitor

图9 基于MnO2/SG的对称型超级电容器的Ragone图(a)和循环稳定性测试(b)

Fig.9 Ragone chart (a) and cycle stability test (b) of MnO2/SG symmetric supercapacitor

表1 二氧化锰和三维石墨烯复合电极材料的性能对比

Table 1 Comparison of capacitance of manganese oxide and three dimensional graphene hybrid materials

电极材料	电流/ (A·g^-1)	比电容量/ (F·g^-1)	文献
MnO₂/3DG	0.25	236	[33]
MnO₂/R-GO@Ni-foam	0.25	267	[34]
MnO₂/Graphene paper	0.5	256	[35]
MnO₂/GH	0.5	293.7	[36]
MnO₂/rGO/Ni foam	0.5	288	[37]
MnO₂/3DHG	0.5	192.2	[38]
MnO₂-rGO-CNTs	0.6	124	[39]
MnO₂/GH	1	200.6	[31]
MnO₂/GA	1	275	[40]
MnO₂/SG	0.5	348.5	this work

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