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    富氮生物质掺氮碳材料的制备及其电化学性能研究

    Preparation and Electrochemical Performance of Nitrogen-Doped Carbon Materials from Nitrogen-Rich Biomass

    • 摘要: 超级电容器作为一种高储能设备,凭借其稳定性强、循环寿命长、充放电速率快、功率密度高、环境适应性良好等优点受到广泛关注。近些年,天然生物质衍生的多孔碳材料因其廉价易得、绿色清洁、可循环再生等优点,被广泛应用于超级电容器领域。以海藻羊栖菜为原料,尿素为氮源,氢氧化钾为活化剂,通过一步碳化−活化法制备了一种具有高比表面积、丰富孔隙结构和适宜含氮量的多孔碳材料。研究结果表明,在碳化温度为700 ℃、羊栖菜与尿素质量比为1∶1的条件下,所制备的多孔碳材料在三电极体系中比电容最大,YN1C-700在0.5 A/g电流密度下比电容达到307.9 F/g,其比表面积高达2 371.07 m2/g。分别在6 mol/L KOH和1 mol/L Na2SO4电解液中组装了对称电容器。在6 mol/L KOH中,YN1C-700在13.37 W·h/kg的能量密度下,功率密度为325 W/kg,经过10 000次充放电循环后,电容保持率为70.45%;在1 mol/L Na2SO4中,当能量密度为20.78 W·h/kg时,功率密度为400.0 W/kg,经过10 000次循环后电容保持率为83.67%。本研究为开发高性能、低成本、环保型的超级电容器电极材料提供了有效策略,同时为海藻资源的高值化利用开辟了新途径。

       

      Abstract: Supercapacitors have garnered significant research interest as advanced energy storage devices due to their remarkable stability, extended cycle life, rapid charge-discharge rates, high power density, and strong environmental adaptability. In recent years, porous carbon materials derived from natural biomass have been widely employed in supercapacitors owing to their cost-effectiveness, eco-friendliness, and renewable nature. In this study, Sargassum fusiforme, a species of seaweed, was used as the primary carbon source, with urea serving as a nitrogen dopant and potassium hydroxide as a chemical activating agent. A one-step carbonization and activation process was utilized to synthesize a nitrogen-enriched porous carbon material characterized by a high specific surface area, well-developed pore structure, and optimized nitrogen content. Among all the prepared seaweed-based carbon materials, the sample synthesized at a carbonization temperature of 800 ℃ with a Sargassum fusiforme to urea mass ratio of 1∶1 (designated as YN1C-800) exhibited the highest specific surface area, reaching 2 494.48 m2/g. However, experimental results indicated that the optimal electrochemical performance was achieved at a carbonization temperature of 700 ℃ with the same mass ratio. The porous carbon prepared under these conditions, denoted as YN1C-700, exhibited a specific capacitance of 307.9 F/g at a current density of 0.5 A/g in a three-electrode configuration and a substantial specific surface area of 2 371.07 m2/g. Structural characterization of YN1C-700 by scanning electron microscopy and Brunauer-Emmett-Teller (BET) analysis revealed a hierarchical porous structure. Furthermore, X-ray photoelectron spectroscopy confirmed the successful incorporation of nitrogen species, with the N 1s spectrum showing a high relative content of N-6 (pyridinic N) and N-5 (pyrrolic N) configurations. To evaluate its practical performance, symmetric supercapacitors were assembled using two different electrolytes: 6 mol/L KOH and 1 mol/L Na2SO4. In the 6 mol/L KOH electrolyte, the device based on YN1C-700 delivered an energy density of 13.37 W·h/kg at a power density of 325.0 W/kg. After 10 000 consecutive charge-discharge cycles, the capacitor retained 70.45% of its initial capacitance. When tested in the 1 mol/L Na2SO4 aqueous electrolyte, the supercapacitor demonstrated improved performance, achieving an energy density of 20.78 W·h/kg at a power density of 400.0 W/kg and exhibiting superior cycling stability with a capacitance retention of 83.67% after 10 000 cycles. These findings suggest that the biomass-derived porous carbon material produced via this facile synthetic route holds great promise for application in high-performance supercapacitors, combining competitive electrochemical properties with the advantages of sustainability and low cost. Moreover, the performance differences between the two electrolytes highlight the critical role of electrolyte selection in optimizing device characteristics. This study provides an effective strategy for developing high-performance, low-cost, and environmentally friendly supercapacitor electrode materials, while opening up a new avenue for the high-value utilization of seaweed resources.

       

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