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    生物质一步法与多步法制备多孔掺氮炭及其电化学应用研究进展

    Research progress on one-step and multi-step methods for preparing porous nitrogen-doped carbon from biomass and its electrochemical applications

    • 摘要: 为契合“双碳”目标,解决直接热解生物炭比表面积小、表面活性官能团匮乏、高价值应用受限的问题,系统地梳理生物质基多孔掺氮炭的制备技术与电化学应用规律,为定向设计与产业化提供理论支撑。以富氮/贫氮生物质为分类依据,对比物理活化与化学活化的优劣及机理,系统探究一步法(同步热解、活化与掺氮)与多步法(热解—活化—掺氮分步进行)的工艺特性;深入分析孔结构(分级多孔构型)与掺氮特性(含氮官能团类型及含量)对电化学性能的构效关系,重点研究材料在超级电容器、氧还原反应电催化及锂/钠离子电池中的应用机制。化学活化(以KOH为代表)比物理活化更易构建高比表面积(最高达3142 m2/g)和分级多孔结构;富氮生物质可通过自掺杂实现氮质量分数最高19.45%,贫氮生物质需外源掺氮,一步法工艺简便但面临“高温活化增强与氮含量降低”的核心矛盾,快速热解技术为孔−氮协同调控提供新路径;多孔掺氮炭凭借分级孔结构与丰富含氮官能团,在超级电容器中实现最高473.5 F/g比电容及99%循环保持率,在氧还原反应(ORR)中展现出媲美Pt/C的催化活性与稳定性,在电池中显著提升离子存储与传输性能。活化与掺氮的协同改性是提升生物质炭性能的关键,一步法是未来低成本制备的主流方向,后续需通过优化工艺参数、揭示反应机理、解决批次稳定性问题,推动其在电化学领域的规模化应用。

       

      Abstract: To align with the “dual carbon” goals and address the inherent limitations of direct pyrolysis biochar—such as low specific surface area, insufficient surface functional groups, and constrained high-value applications—the fabrication techniques and electrochemical applications of biomass-derived nitrogen-doped porous carbon are systematically examined, providing theoretical support for its tailored design and industrial-scale production. Based on the classification of nitrogen-rich and nitrogen-poor biomass precursors, the mechanisms and effectiveness of physical and chemical activation are compared. The process characteristics of one-step methods (simultaneous pyrolysis, activation, and doping) and multi-step methods (sequential pyrolysis, activation, and doping) are systematically analyzed. Furthermore, the structure–performance relationships between hierarchical pore structures, nitrogen doping features (including the types and contents of nitrogen-containing functional groups), and electrochemical properties are thoroughly discussed, with special emphasis on the application mechanisms in supercapacitors, oxygen reduction reaction (ORR) electrocatalysis, and lithium-/sodium-ion batteries. Results indicate that chemical activation, particularly with KOH, outperforms physical activation in constructing high specific surface areas (up to 3142 m2/g) and hierarchical porous structures. Nitrogen-rich biomass can achieve a nitrogen content as high as 19.45% via self-doping, whereas nitrogen-poor biomass requires external nitrogen sources. Although the one-step method is more efficient, it faces a fundamental trade-off between enhanced high-temperature activation and reduced nitrogen retention. Fast pyrolysis technology emerges as a promising approach for the synergistic regulation of pore structure and nitrogen content. Owing to their hierarchical porosity and abundant nitrogen-containing functional groups, these materials exhibit a maximum specific capacitance of 473.5 F/g with 99% cycling retention in supercapacitors, demonstrate ORR activity and stability comparable to those of commercial Pt/C, and significantly improve ion storage and transport in secondary batteries. In summary, the synergistic modification through activation and nitrogen doping is crucial for optimizing biochar performance. The one-step method represents a primary direction for future low-cost production. Subsequent research should focus on optimizing process parameters, elucidating reaction mechanisms, and ensuring batch consistency to facilitate large-scale application in electrochemical energy storage and conversion.

       

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