Template-induced synthesis of CuO-g-C3N4/C composite and its electrochemical property
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摘要: 多价铜基氧化物的理论比容量较高，但自身导电性和稳定性差；石墨相氮化碳(g-C3N4)稳定性好、氮含量高、合成方法简单，但其电容性能不佳；生物质炭具有较大的比表面积、相对较好的导电性和刚性结构。为使各相优势得到充分发挥，并且尽量弥补其缺陷，本文以尿素为g-C3N4前驱体，杏鲍菇为模板诱导合成了具有疏松多孔结构的g-C3N4/C两相复合材料，后使用水热法将CuO均匀负载在g-C3N4/C表面及孔洞内得到CuO-g-C3N4/C三相复合材料。电化学测试结果表明，CuO-g-C3N4/C的最高比电容为262.8F/g，2000次恒电流充放电循环后的电容保持率为97%，在不同电流密度下仍具有良好的充放电性能，CuO-g-C3N4/C的电容性能和稳定性能较好。这表明CuO和g-C3N4/C的三相复合不仅提高了CuO的导电性，而且使g-C3N4的电容性能得到改善，从而使整体材料的储能性能、导电性和稳定性得到提升。Abstract: The theoretical specific capacity of polyvalent copper-based oxides is considerable, but their conductivity and stability are inadequate. Graphite phase carbon nitride (g-C3N4) exhibits good stability, high nitrogen content and simple synthesis method; however, its capacitance performance is poor. Biochar possesses a substantial specific surface area, relatively good electrical conductivity and rigid structure. To fully leverage the advantages of single phase and compensate for their respective shortcomings, a two-phase compound g-C3N4/C with porous structure was synthesized. Urea was served as the precursor of g-C3N4, and pleurorus eryngii was selected as the template. Subsequently, CuO was uniformly anchored on the surface and pores of g-C3N4/C through hydrothermal method, resulting in three-phase CuO-g-C3N4/C. Electrochemical testing reveals that the maximum specific capacitance of CuO-g-C3N4/C reaches 262.8F/g, with a capacitance retention rate of 97% after 2000 constant current charge-discharge cycles. CuO-g-C3N4/C consistently exhibits excellent charge and discharge performance across different current densities, showcasing superior capacitance and stability of CuO-g-C3N4/C. This highlights that the combination of CuO and g-C3N4/C in a three-phase structure not only enhances the conductivity of CuO, but also enhances the capacitive performance of g-C3N4, thereby improving the energy storage performance, electrical conductivity and stability of the overall material.
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Key words:
- g-C3N4 /
- CuO /
- electrochemical /
- biochar /
- template induction /
- supercapacitor
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图 1 不同配比的g-C3N4/C和CuO-g-C3N4/C的XRD图谱
Figure 1. XRD patterns of g-C3N4/C and CuO-g-C3N4/C with different proportions
图 5 50 CuO-2 g-C3N4/C的N2吸附-脱附等温线(a)及其孔径分布(b)
Figure 5. N2 adsorption-desorption isotherm (a) and pore size distribution (b) of 50 CuO-2 g-C3N4/C
图 6 CuO-g-C3N4/C的X射线光电子能谱(XPS)(a)及其Cu 2p(b)，C 1s(c)，N 1s(d)，O 1s(e)的高分辨XPS能谱
Figure 6. X-ray photoelectron spectroscopy (XPS)(a) of CuO-g-C3 N4/C and high-resolution XPS spectra of Cu2p (b), C1s (C), N1s (d), and O 1s(e)
图 7 不同配比的g-C3N4/C和CuO-g-C3N4/C的CV性能测试曲线图
Figure 7. CV performance test curves of g-C3N4/C and CuO-g-C3N4/C with different proportions
图 8 不同配比的g-C3N4/C和CuO-g-C3N4/C的GCD性能测试曲线图
Figure 8. GCD performance test curves of g-C3N4/C and CuO-g-C3N4/C with different proportions
图 9 不同电流密度下g-C3N4/C和CuO-g-C3N4/C的GCD性能测试曲线图
Figure 9. GCD performance test curves of g-C3N4/C and CuO-g-C3N4/C at different current densities
图 10 g-C3N4/C和CuO-g-C3N4/C恒电流充放电性能测试曲线图
Figure 10. Test curve of constant-current charge-discharge performance of g-C3N4/C and CuO-g-C3N4/C
表 1 氧化铜基材料研究进展
Table 1. Research progress of copper oxide based materials
Material Electrolyte Specific capacitance /(F·g−1) Cycling stability Ref. Bi2CuO4//AC 1 mol/L KOH-polyvinyl alcohol (PVA) 94.5 92% 29 Cu2O(Ni(OH)2@Cu2O) 3 mol/L KOH 389.1 70% 30 Cu2O 3 mol/L KOH 79.7 / 30 CuO/ZnO@MWCNT – CZM 3 mol/L KOH 199.4 86.09% 31 CuO NPs 1 mol/L KOH 132 / 32 CuO/NiO/N-rGO 5 mol/L KOH 220 97% 33 CuO-NiO 1 mol/L Na2SO4 35.63 86.7% 34 CuO-g-C3N4/C 3 mol/L KOH 262.8 97 This work Notes: activated carbon (AC)；multiwalled carbon nanotube-cohesive zone model(MWCNT-CZM)；nanoparticles(NPs)；reduced graphene oxide(rGO). Data marked with "/" in the table are not mentioned in the cited literature 
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表 2 样品名称及原料配比
Table 2. Sample names and raw material ratio
Sample name 2g-C3N4/C /g Cu(NO3)2·3H2O NaOH /g 30CuO-2g-C3N4/C 0.07 0.09 0.15 50CuO-2g-C3N4/C 0.05 0.15 0.25 60CuO-2g-C3N4/C 0.04 0.18 0.3 70CuO-2g-C3N4/C 0.03 0.24 0.4 Notes: The prefix "pre-CuO" in the sample nomenclature denotes the mass fraction of CuO in the theoretical calculation relative to the total mass, while the prefix "pre-g-C3N4" represents the mass ratio of g-C3N4 precursors to the pleurorus eryngii template in the g-C3N4/C material. For instance, 50CuO-2g-C3N4/C indicates a three-phase composite material comprising 50% (by weight) CuO and a mass ratio of g-C3N4 precursor to pleurorus eryngii template of 2:1.
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