(Mn7C3, Ni)@C核壳型纳米粒子制备及超级电容器电化学特性

doi:10.15541/jim20160276

无机材料学报 ›› 2017, Vol. 32 ›› Issue (2): 135-140.DOI: 10.15541/jim20160276 CSTR: 32189.14.10.15541/jim20160276

(Mn₇C₃, Ni)@C核壳型纳米粒子制备及超级电容器电化学特性

王玲玲¹, 黄昊¹, Ramon Alberto Paredes Camacho¹, 吴爱民1, 曹国忠^{1, 2}

(1. 大连理工大学材料科学与工程学院, 三束材料改性教育部重点实验室, 大连 116024; 2. 华盛顿大学材料科学与工程学院, 美国 WA98195)

收稿日期:2016-04-25 修回日期:2016-08-23 出版日期:2017-02-20 网络出版日期:2017-01-13
作者简介:王玲玲(1991–), 女, 硕士研究生. E-mail: Wang_LL4585@163.com
基金资助:
国家自然科学基金(51171033);国家中央高校基本科研业务费专项资金(DUT15LAB05, DUT16LAB03)

Preparation and Electrochemical Properties of Core-shell (Mn₇C₃, Ni)@C Nanoparticles

WANG Ling-Ling¹, HUANG Hao¹, Ramon Alberto Paredes Camacho¹, WU Ai-Min¹, CAO Guo-Zhong^{1, 2}

(1. Key Laboratory of Materials Modification by Laser, Ion, and Electron Beams (Ministry of Education), School of Materials Science and Engineering, Dalian University of Technology, Dalian 116024, China; 2. Department of Materials Science and Engineering, University of Washington, Seattle, WA 98195, USA)

Received:2016-04-25 Revised:2016-08-23 Published:2017-02-20 Online:2017-01-13
About author:WANG Ling-Ling. E-mail: Wang_LL4585@163.com
Supported by:
National Natural Science Foundation of China (51171033);The Fundamental Research Funds for the Central Universities(DUT15LAB05, DUT16LAB03)

摘要/Abstract

摘要：

采用直流电弧法, 在CH₄气氛下以钨棒为阴极蒸发锰镍混合物阳极靶材, 制备了(Mn₇C₃, Ni)@C纳米粒子, 并用作超级电容器电极材料。(Mn₇C₃, Ni)@C纳米粒子具有明显的核壳结构, 平均粒径50 nm。在碳外壳包覆下, 内核为Mn₇C₃和Ni的混合物。镍有催化作用, 促进碳源形成, 影响C壳厚度, 锰容易与碳结合生成具有赝电容特性的Mn₇C₃。镍因其催化作用促进碳壳成长, 使纳米粒子具有双电子层电容。Mn-C化合形成的Mn₇C₃具有赝电容特性。因此, 不同锰镍比例对电极电化学性能有极大影响: 锰比例越高, 材料比电容越好(485.12 F/g), 但循环寿命随之变差; 镍比例越高, 材料循环稳定性越好(303.57 F/g), 1000次循环后其比电容保持为原来的70%。

关键词: (Mn7C3, Ni)@C核壳纳米粒子, 电极材料, 直流电弧法, 超级电容器

Abstract:

(Mn₇C₃, Ni)@C nanoparticles were synthesized for electrode material in a supercapacitor. Using DC arc-discharge method, in which the anodic target of Ni-Mn mixture was evaporated in the methane atmosphere by a tungsten cathode. The prepared nanoparticles own a well-defined core/shell structure with average diameter of 50 nm. Encapsulated inside of the carbon shell, the core of the nanoparticles is composed of Mn₇C₃ and Ni. Owing to its catalytic effect, Ni promotes the growth of carbon shell which has the typical double-layer capacitance. Meanwhile Mn₇C₃ as the product of Mn-C reaction is able to provide pseudo-capacitance. The proportion of Ni-Mn in the nanoparticles consequently affects the overall electrochemical performance of the electrodes. The specific capacitance of the electrode increases with the promotion of Mn content (485.12 F/g). The results shows that the nanoparticles with more Ni have better cycle stability (303.57 F/g) and retain 70% of the initial capacitance after 1000 cycles.

Key words: (Mn7C3, Ni)@C core-shell nanoparticles, electrode material, arc-discharge method, supercapacitor

中图分类号:

TK01

王玲玲, 黄昊, Ramon Alberto Paredes Camacho, 吴爱民, 曹国忠. (Mn₇C₃, Ni)@C核壳型纳米粒子制备及超级电容器电化学特性[J]. 无机材料学报, 2017, 32(2): 135-140.

WANG Ling-Ling, HUANG Hao, Ramon Alberto Paredes Camacho, WU Ai-Min, CAO Guo-Zhong. Preparation and Electrochemical Properties of Core-shell (Mn₇C₃, Ni)@C Nanoparticles[J]. Journal of Inorganic Materials, 2017, 32(2): 135-140.

图/表 7

图1 样品1~3的XRD (a)和Raman (b)图谱

Fig. 1 XRD patterns (a) and Raman spectra (b) of sample 1-3Note: Somple 1-3 is Mn:Ni=3:2, 1:1, 2:3, rerpectively

表1 (Mn7C3, Ni)@C核壳型纳米粒子拉曼光谱数据

Table1 Data from Raman spectra of the core-shell (Mn7C3, Ni)@C nanoparticles

	D peak /cm^-1	G peak/cm^-1	I_D / I_G
Sample 1	1348	1577	0.22
Sample 2	1342	1576	0.27
Sample 3	1341	1565	0.60

图2 样品2的XPS图谱

Fig. 2 XPS spectra of sample 2 (Mn:Ni=1:1)

图3 样品1(a, b)、样品2(c, d)和样品3(e, f)的HRTEM和TEM照片

Fig. 3 HRTEM and TEM images of sample 1(a, b), sample 2(c, d), and sample 3(e, f)Note: Somple 1-3 is Mn:Ni=3:2, 1:1, 2:3, rerpectively

表2 (Mn7C3, Ni)@C核壳型纳米粒子的比电容/(F·g-1)

Table 2 Specific capacitance of the core-shell (Mn7C3, Ni)@C nanoparticles / (F·g-1)

v(mV·s^-1)	2	5	10
Sample 1	485.12	448.64	414.54
Sample 2	328.31	299.81	282.99
Sample 3	303.57	297.19	281.25

图4 样品1~3的CV曲线(a~c)(扫描速率分别为2、5、10 mV/s)和样品1~3的DC曲线(d~f)(充放电电流密度分别为2、3、5 A/g)

Fig. 4 CV curves of samples 1-3 at scanning rates of 2, 5, 10 mV/s(a-c), and DC curves of samples 1-3 at charge and discharge current densities of 2, 3, 5 A/g(d-f)Note: Somple 1-3 is Mn:Ni=3:2, 1:1, 2:3, rerpectively

图5 样品1~3的循环寿命曲线(a)和能量密度与功率密度柱形图(b)

Fig. 5 Cycle stability curves (a) and histograms of energy and power densities (b) of samples 1-3Note: Somple 1-3 is Mn:Ni=3:2, 1:1, 2:3, rerpectively

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(Mn₇C₃, Ni)@C核壳型纳米粒子制备及超级电容器电化学特性

Preparation and Electrochemical Properties of Core-shell (Mn₇C₃, Ni)@C Nanoparticles

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