在我国“双碳”战略目标驱动下，开发高效电催化体系与长寿命电化学能源器件已成为缓解化石能源依赖的核心路径。直接硼氢化物燃料电池（DBFC）凭借其高理论能量密度和碱性环境适配性，在能源存储与转换领域展现出独特的发展潜力。然而DBFC常常使用铂族贵金属催化剂，铂族贵金属存在价格高和易中毒的缺点，因此DBFC的大规模应用受到了限制。于是，开发低成本、高效率和持久耐用的非贵金属电催化剂成为推进DBFC商业化进程的关键。本文致力于DBFC非贵金属电催化剂的制备及其性能研究，通过调控材料特性和制备方法，在催化活性与稳定性方面取得了一定进展。本文主要针对以下几种催化剂进行了研究分析：

（1）为解决DBFC阴极氧还原反应（ORR）动力学缓慢和长期稳定性不足的问题，设计了以碳纳米管为基底的CeO₂-p/CNTs阴极催化剂。采用沉淀法和低温等离子体技术（Plasma）对CeO₂纳米颗粒进行了改性并制备了CeO₂-p/CNTs阴极催化剂。CeO₂-p/CNTs催化剂对ORR表现出良好的电催化活性和稳定性，具有较高的半波电位（0.868 V vs. Hg/HgO），低内阻（0.125 Ω cm^-2）和低Tafel斜率（299 mV dec^-1）。以CeO₂-p/CNTs为阴极，Pt/C为阳极的DBFC显示出优异的性能，其开路电压（OCP）为1.19 V，峰值功率密度达到199.34 mW cm^-2，并且具有良好的稳定性。Plasma处理增加了材料的介孔结构，提升了其比表面积，在表面产生氧空位。除此之外，通过微观形貌分析，证明了CeO₂纳米颗粒更多地负载在了CNTs的端点和管壁上，进而增加了活性位点的数量。这项工作为合理设计燃料电池高效非贵金属阴极催化剂提供了一种新方法。

（2）为解决DBFC阳极硼氢根离子氧化反应（BOR）导致的催化活性低的问题，设计了具有氧空位的p-Co(OH)₂纳米片催化剂，提高了催化剂的活性。通过物理表征和电化学表征研究了Plasma处理条件对催化剂活性的影响，并且在Plasma辅助化学还原法的制备方法中探究出Plasma最佳处理条件为40 V，8 min，O₂:N₂=2:5。在BOR反应过程中，p-Co(OH)₂/2.96-O₂/N₂催化剂展现出了最佳的性能，BOR的最高电流密度为58 mA cm^-2。该催化剂应用于DBFC的阳极，其OCP为1.17 V，在室温下达到244 mW cm^-2的峰值功率密度，且经过210 h的稳定性测试，电池没有明显的衰减，这表明组装的DBFC具有优良的催化活性和良好的工作稳定性。同样表明Plasma对提高催化剂性能有着关键作用，改性后的催化剂在结晶度和表面形貌均有改变，具有氧空位和较窄的能带间隙，其中氧空位可增加高密度的活性位点，窄的能带隙可加速电子跳跃，从而提高电子转移的速度，进一步提高催化活性。

（3）为解决DBFC阳极催化剂在高电流密度下稳定性差的问题，在高活性的p-Co(OH)₂催化剂的基础上，设计了Co(OH)₂/Co₃O₄复合催化剂，进一步提高催化剂稳定性。采用Plasma和水热法协同制备，并调控氢氧化钾（KOH）的用量引入Co₃O₄制备了Co(OH)₂/Co₃O₄催化剂。经过测试，KOH用量为2 M，即2-Co(OH)₂/Co₃O₄催化剂具有最佳的BOR催化活性，BOR电流密度高达77.76 mA cm^-2，CV面积最大，Tafel斜率低至193.05 mV dec^-1，并且稳定工作100 h后衰减仅2%。2-Co(OH)₂/Co₃O₄催化剂组装的DBFC显示出优异的性能，其OCP为1.10 V，峰值功率密度为279.01 mW cm^-2，在40 mA cm^-2的恒定电流下稳定工作100 h，并无衰减。其中，Co(OH)₂纳米片具有层状结构和充足的比表面积，Co₃O₄纳米颗粒的加入提供了更多的活性位点数量，同时纳米颗粒的分散提升了表面反应动力学。进而加速催化反应的进程，提高催化活性。

             Driven by China’s strategic goals, the development of high-efficiency electrocatalytic systems and long-lasting electrochemical energy devices has become a critical pathway to reduce reliance on fossil fuels. Direct borohydride fuel cell (DBFC) demonstrate unique potential in energy storage and conversion due to their high theoretical energy density and alkaline environment adaptability. However, the widespread application of DBFC has been constrained by the prevalent use of platinum-based noble metal catalysts, which suffer from high costs and susceptibility to poisoning. Consequently, developing cost-effective, highly efficient, and durable non-precious metal electrocatalysts has become pivotal for advancing DBFC commercialization. This study focuses on the preparation and performance investigation of non-precious metal electrocatalysts for DBFCs, achieving notable progress in catalytic activity and stability through material property regulation and synthesis method optimization. The following catalysts were systematically investigated:

(1) The CeO₂-p/CNTs catalyst was synthesized by loading CeO₂ nanoparticles onto carbon nanotubes (CNTs) followed by low-temperature plasma modification to address sluggish oxygen reduction reaction (ORR) kinetics and insufficient long-term stability at DBFC cathodes. The catalyst demonstrated exceptional ORR activity, with a high half-wave potential of 0.868 V vs. Hg/HgO, a low Tafel slope of 299 mV dec^-1, and a minimal internal resistance of 0.125 Ω cm^-2. DBFC using CeO₂-p/CNTs as the cathode catalyst exhibited outstanding performance: an open-circuit potential (OCP) of 1.19 V, a peak power density of 199.34 mW cm^-2, and excellent stability. Plasma treatment enhanced the mesoporous structure and specific surface area of the material, improving active site exposure. Microscopic analysis confirmed that CeO₂ nanoparticles were preferentially anchored at the tips and sidewalls of CNTs, increasing active site density. This work provides a novel strategy for designing efficient non-precious metal cathode catalysts for fuel cells.

(2) The p-Co(OH)₂ nanosheet catalyst with oxygen vacancy-rich was designed to overcome low catalytic activity in borohydride oxidation reaction (BOR) at DBFC anodes. Systematic investigation of plasma treatment parameters (40 V,8 min,O₂:N₂=2:5) through physicochemical characterization revealed optimal conditions. The optimized p-Co(OH)₂/2.96-O₂/N₂ catalyst achieved maximum BOR current density of 58 mA cm^-2. The corresponding DBFC demonstrated an OCP of 1.17 V, peak power density of 244 mW cm^-2 at room temperature, and stable operation over 210 h without significant decay. Plasma modification induced crystallographic and morphological changes, creating oxygen vacancies and narrowing bandgap. These structural advantages enhanced active site density and accelerated electron transfer, thereby improving catalytic performance.

(3) The Co(OH)₂/Co₃O₄ composite catalyst was synthesized via plasma and hydrothermal methods with controlled reductant concentrations to address stability challenges under high current densities. The 2-Co(OH)₂/Co₃O₄ catalyst (using 2 M KOH) exhibited optimal BOR performance: a current density of 84 mA cm^-2, the largest CV area, a low Tafel slope (192 mV dec⁻¹), and minimal decay (2%) over 100 h of operation. DBFCs assembled with this catalyst achieved an OCP of 1.10 V and a peak power density of 279.01 mW cm^-2. The layered structure of Co(OH)₂ nanosheets provided abundant exposed active sites, while Co₃O₄ nanoparticles enhanced surface reaction kinetics through dispersed active sites, synergistically accelerating catalytic processes.

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