馄饨结构的KB@Co-C3N4在中性电解质中作为锌空气电池的高活性和稳定性氧催化剂

doi:10.1016/S1872-2067(23)64639-X

摘要/Abstract

摘要： 本文解决了氧在中性介质中催化应用所面临的挑战, 包括缓慢的动力学和严重的碳腐蚀问题. 为克服这些问题, 利用氮化碳(g-C₃N₄)支撑Co-Nx活性位点并同时包覆科琴黑(KB)形成馄饨结构, 研发了一种双功能氧催化剂(KB@Co-C₃N₄). 所得催化剂在中性电解质中表现出优异的氧还原反应/析氧反应(ORR/OER)活性和良好的稳定性. KB@Co-C₃N₄催化剂表现出0.723 V的半波电位(E_1/2), 经过40000圈ORR加速耐久性测试(ADT)后仅有9 mV的衰减. 在OER方面, KB@Co-C₃N₄在10 mA cm^-2(ŋ₁₀)处的过电位为550 mV, 在20000圈OER ADT后几乎没有增加. 采用KB@Co-C₃N₄的锌空气电池在开路电压(1.52 V)、恒流放电/充电性能和循环持续时间(985 h在5 mA cm^-2)方面均表现出优越性能. 理论研究揭示了金属活性位点的工程电子结构使得对Co中心的电荷分布进行精确调控, 从而优化氧化中间体的吸附和脱附. 催化剂的高稳定性归因于化学稳定的C₃N₄, 它强化了Co-Nx活性位点并通过包覆KB形成馄饨结构保护KB免受碳腐蚀.
本文首先将剥离的C₃N₄与KB混合后煅烧得到C₃N₄包覆的KB材料(KB@C₃N₄), 随后再次煅烧将Co单原子引入KB@C₃N₄中, 形成高活性和稳定性的KB@Co-C₃N₄氧催化剂. 红外光谱分析证实了KB@Co-C₃N₄中存在C₃N₄成分. 透射电镜和元素标记显示C₃N₄均匀包覆在KB基底上. 通过同步辐射测试确定了Co单原子的配位环境为CoN₄结构. 在0.5 M NH₄Cl溶液中测试了其ORR/OER催化活性和稳定性. KB@Co-C₃N₄在ORR方面表现出卓越性能, 半波电位为0.723 V, 显著优于商业铂碳催化剂(0.673 V)和普通Co-N-C催化剂(0.694 V). 经过40000圈加速耐久性测试后, KB@Co-C₃N₄仅衰减9 mV, 而商业铂碳和Co-N-C经过7500圈测试后分别衰减41和44 mV. 在OER方面, KB@Co-C₃N₄在10mA cm^-2时的过电位为550 mV, 优于氧化钌的560 mV和Co-N-C的600 mV. 经过20000圈测试后, KB@Co-C₃N₄的OER过电位几乎未变化, 而氧化钌和Co-N-C经过4000圈测试后分别增加了37和20 mV. 实验前后的透射电镜图显示KB@Co-C₃N₄的形貌未发生明显变化, 表明其出色的稳定性. 理论计算结果显示, 通过C₃N₄优化Co金属活性位点的电子结构, 可优化Co中心的电荷分布并强化Co-N键, 而化学稳定的C₃N₄对KB基底的包覆可以在高电位下有效避免KB腐蚀, 使KB@Co-C₃N₄具有卓越稳定性和催化活性. 在中性锌空气电池应用中, 使用KB@Co-C₃N₄的电池拥有1.52 V的开路电压, 并且在5 mA cm^-2的高电流密度下稳定循环超过985 h, 优于已报道的其他使用碳基材料作为阴极催化剂的中性锌空气电池.
综上所述, 馄饨结构的KB@Co-C₃N₄具有优异的氧催化活性和稳定性, 为设计高稳定性高活性的M-N-C催化剂提供了重要参考.

关键词: 氧电催化, 单原子催化剂, 中性电解液, 抗腐蚀

Abstract: This work addresses the challenges faced by oxygen catalysis applications in neutral media, which are hindered by sluggish kinetics and severe carbon corrosion. To overcome these issues, a bifunctional oxygen catalyst (KB@Co-C₃N₄) was developed by utilizing graphitic carbon nitride (g-C₃N₄) to support Co-N_x active sites and simultaneously to wrap Ketjen black (KB) to form a wonton structure. The resulting catalyst exhibited excellent ORR/OER activity and good stability in neutral electrolytes. The KB@Co-C₃N₄ catalyst demonstrated a half-wave potential (E_1/2) of 0.723 V and only a 9 mV decay after 40000 cycles of ORR accelerated durability test (ADT). In terms of OER, the overpotential at 10 mA cm^-2 (ŋ10) of KB@Co-C₃N₄ was 550 mV, with negligible increase observed even after 20k cycles of OER ADT. The zinc-air battery incorporating KB@Co-C₃N₄ exhibited superior performances over other benchmark bifunctional counterparts in open-circuit voltage (1.52 V), galvanostatic discharge/charge performance and cycling duration (985 h at 5 mA cm^-2). The theoretical investigation revealed that the engineered electronic structures of the metal active sites enable precise regulation of the charge distribution of Co centers, leading to optimized adsorption and desorption of oxygenated intermediates. The high stability of the catalyst is attributed to the chemically stable C₃N₄, which strengthens Co-N_x active sites and protects KB against carbon corrosion by wrapping KB to form the wonton structure.

Key words: Oxygen electrocatalysis, Single-atomic catalysts, Neutral electrolyte, Corrosion resistance

吴维凡, 范晋歌, 赵振宏, 潘建敏, 杨静, 阎兴斌, 詹怡. 馄饨结构的KB@Co-C₃N₄在中性电解质中作为锌空气电池的高活性和稳定性氧催化剂[J]. 催化学报, DOI: 10.1016/S1872-2067(23)64639-X.

Wei-Fan Wu, Jin-Ge Fan, Zhen-Hong Zhao, Jian-Min Pan, Jing Yang, Xingbin Yan, Yi Zhan. Wonton-structured KB@Co-C₃N₄ as a highly active and stable oxygen catalyst in neutral electrolyte for Zinc-air battery[J]. Chinese Journal of Catalysis, DOI: 10.1016/S1872-2067(23)64639-X.

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馄饨结构的KB@Co-C₃N₄在中性电解质中作为锌空气电池的高活性和稳定性氧催化剂

Wonton-structured KB@Co-C₃N₄ as a highly active and stable oxygen catalyst in neutral electrolyte for Zinc-air battery

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