Preparation of Fe2O3/nitrogen-doped biomass carbon composites and their application in supercapacitors
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摘要:
Fe2O3/ 氮掺杂生物质碳复合材料制备及其在超级电容器中的应用 生物质衍生碳材料以其来源广泛、可再生、环境友好、较好的导电性与高表面积等优势应用于超级电容器中，但其比电容、能量密度较低影响了它的实际应用。在此，本文将生物质废弃物转化为具有良好化学性质的碳材料，并通过杂原子掺杂生物质碳材料与过渡金属氧化物Fe2O3进行复合，利用Fe2O3与氮掺杂碳的互补优势，以一步碳化法制备出Fe2O3/氮掺杂生物质碳复合材料，表现出优异的电化学性能。结果表明：Fe2O3/NBCs作为负极材料在1 A·g-1电流密度下的比电容为575 F·g-1。同时，将Fe2O3/NBCs-700°C和NiCoFe-P分别为负极和正极材料组装成不对称超级电容器，在功率密度为800 W·kg-1的情况下，能量密度达到33.3 W·h·kg-1。组装的不对称超级电容器还表现出优异循环稳定性，经过3500次循环后仍保持82.4%的电容。 图 (a)比电容与电流密度的函数关系;(b)能量密度 Abstract: The development of renewable, low-cost and environmentally friendly electrode materials with fast ion/electron transfer rate and adjustable surface chemistry is an urgent need for the development of current energy storage devices. In recent years, biomass carbon materials have attracted much attention because of their low cost, renewable and good cycling performance, but their low specific capacitance and energy density affect their practical applications. Here, the biomass waste was transformed into carbon materials with good chemical properties, and the transition metal oxide Fe2O3 was composite by heteroatom-doped biomass carbon materials, taking advantage of the complementary strengths of Fe2O3 and nitrogen doped carbon was used to prepare Fe2O3/ nitrogen-doped biomass carbon (NBCs) composite materials by one-step carbonization, showing excellent electrochemical performance. The results show that the specific capacitance of Fe2O3/NBCs as the negative electrode material is 575 F·g−1 at a current density of 1 A·g−1. At the same time, Fe2O3/NBCs-700°C and NiCoFe-P were used as cathode and cathode materials respectively to assemble asymmetric supercapacitors, achieves an energy density of 33 W·h·kg−1 at a power density of 800 W·kg−1. The assembled asymmetric supercapacitors also exhibit excellent cycling stability, maintaining 82.35% capacitance after 3500 cycles. Therefore, Fe2O3/NBCs is a promising electrode material for supercapacitors as negative electrode materials.-
Key words:
- biomass /
- Fe2O3 /
- Nitrogen doping /
- Composite material /
- Supercapacitor /
- Electrode material /
- energy storage
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图 1 Fe2O3/氮掺杂生物质碳(NBCs)制备示意图。
Figure 1. Schematic diagram of the preparation of Fe2O3/ nitrogen-doped biomass carbon (NBCs).
图 2 ((a)、(b)、(c)) Fe2O3/NBCs-700°C不同倍数下的SEM图像；(d) Fe2O3/NBCs-700°C的EDS元素映射图；((e)、(f)、(g)) Fe2O3/NBCs-700°C不同倍数下的TEM图像。
Figure 2. ((a)、(b)、(c)) SEM images of Fe2O3/NBCs-700°C under different multiples; (d) EDS element map of Fe2O3/NBCs-700°C; ((e)、(f)、(g)) TEM images of Fe2O3/NBCs-700°C at different multiples.
图 3 (a) 所有样品的XRD图谱；(b) Fe2O3/NBCs-700°C的Raman图像；(c) Fe2O3/NBCs-700°C的氮气吸附解析曲线；(d) Fe2O3/NBCs-700°C的孔径分布曲线。
Figure 3. (a) XRD patterns of all samples; (b) Raman images of Fe2O3/NBCs-700°C; (c) Nitrogen adsorption analytical curve of Fe2O3/NBCs-700°C; (d) Pore size distribution curve of Fe2O3/NBCs-700°C.
图 4 (a) Fe2O3/NBCs-700°C的全范围XPS光谱图；(b) Fe2O3/NBCs-700°C的Fe 2 p光谱；(c) Fe2O3/NBCs-700°C的C 1 s光谱；(d) Fe2O3/NBCs-700°C的N 1 s光谱。
Figure 4. (a) Full range XPS spectrum of Fe2O3/NBCs-700°C; (b) Fe 2 p spectra of Fe2O3/NBCs-700°C; (c) C 1 s spectra of Fe2O3/NBCs-700°C; (d) N 1 s spectra of Fe2O3/NBCs-700°C.
图 5 (a) 不同条件电极材料在三电极体系中10 mV·s−1扫描速率下的CV曲线；(b) Fe2O3/NBCs-700°C在不同扫描速率下的CV曲线；(c) 不同条件电极材料在1 A·g−1电流密度下的GCD曲线；(d) Fe2O3/NBCs-700°C在不同电流密度下的GCD曲线。
Figure 5. (a) CV curves of electrode materials under different conditions at 10 mV·s−1 scanning rate in three electrode system; (b) CV curves of Fe2O3/NBCs-700°C under different scanning rates; (c) GCD curves of electrode materials under different conditions at 1 A·g−1 current density; (d) GCD curves of Fe2O3/NBCs-700°C at different current densities.
图 6 (a) 比电容与电流密度的函数关系；(b) Nyquist曲线。
Figure 6. (a) The functional relationship between specific capacitance and current density; (b) Nyquist curve.
图 7 (a)、(b) 、(c)、(d) NiCoFe-P不同倍数下的TEM图像。
Figure 7. (a)、(b) 、(c)、(d) TEM images of NiCoFe-P at different multiples.
图 9 (a) NiCoFe-P的氮气吸附解析曲线；(b) NiCoFe-P的孔径分布曲线。
Figure 9. (a) Nitrogen adsorption analysis curve ofNiCoFe-P; (b) Pore size distribution curve of NiCoFe-P.
图 10 (a) NiCoFe-P的全范围XPS谱图；(b) NiCoFe-P的Ni 2 p光谱；(c) NiCoFe-P的Co 2 p光谱；(d) NiCoFe-P的Fe 2 p光谱。
Figure 10. (a) full range XPS spectrum of NiCoFe-P; (b) Ni 2 p spectra of NiCoFe-P; (c) Co 2 p spectra of NiCoFe-P; (d) Fe 2 p spectra of NiCoFe-P.
图 11 (a) NiCoFe-P在三电极体系中不同扫描速率下的CV曲线；(b) NiCoFe-P在不同电流密度下的GCD曲线；(c) 比电容与电流密度的函数关系；(d) Nyquist曲线。
Figure 11. (a) CV curves of NiCoFe-P at different scanning rates in three electrode system; (b) GCD curves of NiCoFe-P at different current densities; (c) The functional relationship between specific capacitance and current density; (d) Nyquist curve.
图 12 (a) Fe2O3/NDCs-700°C//NiCoFe-P不对称超级电容器结构示意图；(b)不同电压区间的CV曲线；(c)不同扫描速率下的CV曲线；(d)不同电流密度下的GCD曲线。
Figure 12. (a) Structural diagram of Fe2O3/NDCs-700°C//NiCoFe-P asymmetric supercapacitor; (b) CV curves of different voltage intervals; (c) CV curves at different scanning rates; (d) GCD curves at different current densities.
图 13 (a)比电容与电流密度的函数关系；(b) Ragone图；(c) 在10 A·g-1下的循环性能；(d) Nyquistqt曲线。
Figure 13. (a) Is a function of specific capacitance and current density; (b) Ragone diagram; (c) Cycle performance at 10 A·g-1; (d) Nyquistqt curve
表 1 XPS测定Fe2O3/NBCs-700°C样品中的元素含量。
Table 1. Determination of element content in Fe2O3/NBCs-700°C samples by XPS.
Materials C N O Fe Fe2O3/NBCs-700°C 47.52% 7.48% 41.29% 3.72% 
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表 2 用XPS法测定NiCoFe-P样品中的元素含量
Table 2. Determination of element content in NiCoFe-P samples by XPS.
Materials C O P Fe Co Ni NiCoFe-P 24.60% 53.86% 17.17% 1.87% 1.94% 0.55%
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