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基于可逆相变机制的高稳定性MnO纳米线@C@MnO纳米片核壳异质结构赝电容电极

High-Stability MnO Nanowires@C@MnO Nanosheet Core-Shell Heterostructure Pseudocapacitance Electrode Based on Reversible Phase Transition Mechanism.

作者信息

Ma Zhipeng, Jing Fengyang, Fan Yuqian, Hou Liyin, Su Li, Fan Lukai, Shao Guangjie

机构信息

Hebei Key Laboratory of Applied Chemistry, College of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao, 066004, China.

State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, 066004, China.

出版信息

Small. 2019 May;15(20):e1900862. doi: 10.1002/smll.201900862. Epub 2019 Apr 18.

DOI:10.1002/smll.201900862
PMID:30997956
Abstract

A stable MnO @C@MnO core-shell heterostructure consisting of vertical MnO nanosheets grown evenly on the surface of the MnO @carbon nanowires are obtained by simple liquid phase method combined with thermal treatment. The hierarchical MnO @C@MnO heterostructure electrode possesses a high specific capacitance of 350 F g and an excellent cycle performance owing to the existence of the pore structure among the ultrasmall MnO nanoparticles and the rapid transmission of electrons between the active material and carbon coating layer. Particularly, according to the in situ Raman spectra analysis, no characteristic peaks corresponding to MnOOH are found during charging/discharging, indicating that pseudocapacitive behavior of the MnO electrode have no relevance to the intercalation/deintercalation of protons (H ) in the electrolyte. Further combining in situ X-ray powder diffraction analysis, the diffraction peak of α-MnO can be detected in the process of charging, while Mn O phase is found in discharge products. Therefore, these results demonstrate that the MnO undergoes a reversible phase transformation reaction of Mn O ↔α-MnO . Moreover, the assembled all-solid-state asymmetric supercapacitor with a MnO @C@MnO electrode delivers a high energy density of 23 Wh kg , an acceptable power density of 2500 W kg , and an excellent cyclic stability performance of 94% after 2000 cycles, showing the potential for practical application.

摘要

通过简单的液相法结合热处理,获得了一种稳定的MnO@C@MnO核壳异质结构,该结构由均匀生长在MnO@碳纳米线表面的垂直MnO纳米片组成。分级MnO@C@MnO异质结构电极具有350 F g的高比电容和优异的循环性能,这归因于超小MnO纳米颗粒之间存在孔隙结构以及活性材料与碳涂层之间电子的快速传输。特别地,根据原位拉曼光谱分析,在充电/放电过程中未发现对应于MnOOH的特征峰,这表明MnO电极的赝电容行为与电解质中质子(H⁺)的嵌入/脱嵌无关。进一步结合原位X射线粉末衍射分析,在充电过程中可检测到α-MnO的衍射峰,而在放电产物中发现了Mn₂O₃相。因此,这些结果表明MnO经历了Mn₂O₃↔α-MnO的可逆相变反应。此外,采用MnO@C@MnO电极组装的全固态不对称超级电容器具有23 Wh kg的高能量密度、2500 W kg的可接受功率密度以及2000次循环后94%的优异循环稳定性,显示出实际应用的潜力。

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