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摘要: 金属空气电池作为高效的能源转换与存储装置，受到人们广泛关注。然而，阴极反应动力学缓慢及贵金属高昂的成本等一系列问题严重制约了金属空气电池的实用化进程。生物质炭材料因其特殊的电化学性能、环境效益和经济价值，已成为开发高性能金属空气电池阴极材料的重要选择。近年来，生物质炭材料在材料制备和微观结构设计等方面取得了较大进展。本文综述了生物质炭材料在金属空气电池阴极应用的最新研究进展，并从反应机理、合成策略和多维结构（一维、二维和三维）的角度深入阐述其对电催化性能的影响。最后，进一步讨论了生物质炭材料面临的挑战和未来的发展方向。这篇综述为生物质炭材料的结构设计提供了新的视角，旨在为开发高效、廉价和稳定的金属空气电池阴极催化剂提供参考和借鉴。Abstract: Metal-air batteries have received significant attention as highly efficient energy conversion and storage devices. Nevertheless, several difficulties, such as the sluggish reaction kinetics of the cathode and the high cost of precious metals, have significantly hampered their commercialization. Biomass carbon materials have emerged as an important alternative for the development of high-performance cathode materials in metal-air batteries, owing to their remarkable electrochemical characteristics, environmental friendliness and cost effectiveness. In recent years, there has been huge progress in the preparation and design of biomass carbon materials. This review summarizes the most recent research on these materials, and the effects of the reaction mechanism, synthesis method and multidimensional (1D, 2D, 3D) structure on their electrocatalytic performance are reviewed. Finally, problems associated with their use and possible new developments are discussed. The review presents new perspectives on the structure of these materials, and provides a basis for the development of efficient, affordable, and stable cathode materials for metal-air batteries.
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Key words:
- Biomass /
- Carbon materials /
- Metal-air battery /
- Cathode /
- Electrocatalysis
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图 1 生物质炭材料合成策略及应用示意图
Figure 1. Synthesis strategy and application diagram of biomass carbon material
图 2 ORR和OER的作用机制和途径（红色：碱性，蓝色：酸性）
Figure 2. Mechanism and pathway of ORR and OER (red: alkaline, blue: acidic)
图 3 (a) BC生物质炭合成示意图[54]；(b) N2的吸附-解吸等温线[54]；(c) Ni/CNF-750放电极化与其功率密度曲线[54]；(d) Ni/CNF-750充放电循环耐久性测试[54]；(e) 羊毛生物质炭合成示意图[56]；(f) 不同转速下的LSV曲线及K-L图[56]
Figure 3. (a) Synthesis diagram of BC biomass char[54], (b) N2 adsorption-desorption isotherms[54], (c) Ni/CNF-750 discharge polarization and its power density curve[54], (d) Ni/CNF-750 charge/discharge cycle durability[54], (e) Synthesis diagram of wool biomass carbon[56], (f) LSV curves and K-L plots at different speeds[56]. Reprinted with permission
图 4 (a) 纤维素炭材料的合成过程[58]；(b) FexNiyN@C/NC催化剂和(c)TEM照片[58]；(d) FexNiyN@C/NC和Pt/C在0.7 V时随时间变化图，插图：CV1000次循环前后FexNiyN@C/NC的OER极化图[58]；(e) 海藻合成多孔炭的示意图[61]；(f) 不同氮含量的催化剂的ORR效果图[61]
Figure 4. (a) Synthesis process of cellulose carbon materials[58]. (b) FexNiyN@C/N Catalyst and (c) TEM images[58]. (d) Chronoamperometric responses of FexNiyN@C/NC and Pt/C at 0.7 V, inset: OER of FexNiyN@C/NC before and after 1000 cycles of CV between 1.3 and 1.6 V[58]. (e) Diagram of a synthetic porous carbon from seaweed[61]. (f) Graph of ORR effect of catalysts with different nitrogen content[61]. Reprinted with permission
图 5 (a) 花生壳衍生炭材料合成路线示意图[67]；(b) PS-800-100催化剂N2吸附-解吸曲线与(c) 孔径分布图[67]； (d) 茄子衍生炭材料合成过程[68]；(e) 女贞子果实合成纳米片合成过程[69]；(f) GPNCS的形成机理[69]；(g) GPNCS纳米片SEM图像[69]；(h) GPNCS的N2吸附-解吸图与(i) 孔径分布图[69]
Figure 5. (a) Diagram of the synthesis route of peanut shell-derived carbon materials[67]. (b) N2 adsorption-desorption curve and (c) pore size distribution of GPNCS[67]. (d) Synthesis process of eggplant-derived carbon material[68]. (e) Synthesis process of chasteberry fruit synthetic nanosheets[69]. (f) Mechanism of GPNCS formation[69]. (g) SEM image of GPNCS nanosheet[69]. (h) N2 adsorption-desorption diagram and (i) pore size distribution PS-800-100 catalyst[69]. Reprinted with permission
图 6 (a) 浸渍前细菌纤维素SEM照片与(b) 浸渍后SEM照片[84]; (c) 不同电流密度下的放电曲线[84]; (d)和(e) 海藻衍生炭D-CFs的SEM照片[85]；(f) D-CFs-、N/S-CFs-和Pt/C基锌空气电池的静电放电曲线[85]；(g) Fe2N@NCNTs催化剂TEM照片[82]；(h) Fe2N@NCNTs阴极在不同转速下的LSV曲线[82]；(i) Fe2N@NCNTs放电极化及其功率密度曲线[82]；(j) 狼尾草衍生炭催化剂Fe2-N/CNTs-850 °C的TEM照片[83]；(k) 不同狼尾草衍生炭与Pt/C催化剂起始电位与半波电位汇总图[83]；(l) Fe2-N/CNTs-850 °C的CV曲线[83]
Figure 6. (a) SEM image of bacterial cellulose before impregnation and (b) SEM image after impregnation[84]. (c) Discharge curves at different current densities[84]. (d, e) SEM image of algal-derived carbon D-CFs[85]. (f) Electrostatic discharge curves of D-CFs-, N/S-CFs- and Pt/C-based zinc-air batteries[85]. (g) TEM image of Fe2N@NCNTs catalyst[82]. (h) LSV curves of Fe2N@NCNTs cathodes at different speeds[82]. (i) Discharge polarization of Fe2N@NCNTs and their power density curves[82]. (j) TEM image of wolfsbane derived carbon catalysts Fe2-N/CNTs-850 °C[83]. (k) Starting and half-wave potentials of different wolfsbane derived carbon and Pt/C catalysts[83]. (l) CV curves of Fe2-N/CNTs-850 °C[83]. Reprinted with permission
图 7 (a) 蔓越莓豆壳衍生炭（C-cranberry)SEM照片与(b)TEM照片[98]；(c, d) 麦秸衍生炭（AC-HC）TEM照片[101]；(e) 猪血衍生炭纳米片（Zn/FeSA-PC/950/NH3）TEM照片与(f) SEM照片[102]
Figure 7. (a) SEM images and (b) TEM images[98] of cranberry bean shell-derived carbon (C-cranberry). (c-d) TEM images of wheat straw-derived carbon (AC-HC)[101]. (e) TEM image of pig blood-derived carbon nanosheets (Zn/FeSA-PC/950/NH3) with (f) SEM image[102]. Reprinted with permission
图 8 (a) 巴沙木与(b) 脱木质素后SEM照片[106]；(c) FeCo@NS-CA催化剂与Pt/C催化剂的比容量曲线[106]；(d) 松果衍生碳SEM照片[108]；(e) 松果衍生炭材料SEM照片及性能图[108]；(f) 稻壳多孔炭SEM照片[110]；(g) Si-Fe/S/N-RH3催化剂的元素映射图像[110]
Figure 8. SEM images of (a) balsa wood and (b) post delignification sample[106]. (c) Specific capacity curves of FeCo@NS-CA catalysts versus Pt/C catalysts[106]. (d) SEM image of pine cone derived carbon[108]. (e) SEM image and properties of pine cone derived carbon materials[108]. (f) SEM image of rice husk porous carbon[110]. (g) Elemental mapping images of Si-Fe/S/N-RH3 catalysts[110]. Reprinted with permission
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