Job-synergistic engineering from Fe3N/Fe sites and sharp-edge effect of hollow star-shaped nitrogen-doped carbon structure for high-performance zinc-air batteries
Job-synergistic engineering from Fe3N/Fe sites and sharp-edge effect of hollow star-shaped nitrogen-doped carbon structure for high-performance zinc-air batteries
复制标题
DOI：
10.1016/j.carbon.2023.118333
复制
发表时间：
2023-07
期刊：
影响因子：
10.9
通讯作者：
Kaixin Wang;Chao Qiu;Zhengyi Wang;Qilan Chen;Jiajie Pan;Junhao Li;Ming Wu;Huafeng Dong
中科院分区：
文献类型：
--
作者：
Kaixin Wang;Chao Qiu;Zhengyi Wang;Qilan Chen;Jiajie Pan;Junhao Li;Ming Wu;Huafeng Dong
由于贵金属催化剂来源有限、成本高、长期稳定性差等问题，限制了锌空气电池的大规模商业化应用。因此，设计具有优异的氧还原反应（ORR）和析氧反应（OER）活性和稳定性的非贵金属催化剂的研究方兴未艾。在此，我们报道了一种中空星形双功能电催化剂，其具有均匀分散的Fe 3 N/Fe纳米颗粒，通过简单的牺牲模板策略从沸石咪唑骨架（ZIFs）衍生而来。这种中空结构具有密度低、壳层薄、渗透性高的特点，其内部空腔不仅提供了额外的三相界面，加速了O2的还原和析出，而且促进了反应物向催化剂上的扩散。通过控制铁金属盐的投加量，可以有效调节FeNP的分散程度，生成的Fe 3 N引入丰富的Fe-Nx活性位。密度泛函理论计算表明，Fe 3 N和FeNP之间的强亲和力有利于促进氧中间体反应，实现作业协同催化效应和较高的反应动力学。合成的Fe 3 N/FeNP-N-C-3.3%表现出优异的OER和ORR双功能活性，ORR具有0.867 V的高半波电位（优于0.82 V的市售Pt/C），在10 mA cm−2下OER的过电位仅为294 mV。用Fe 3 N/FeNP-N-C-3.3%作为空气阴极制备的可再充电锌空气电池显示出超过750小时的长期循环性能和205 mW cm-2的最大功率密度。柔性锌空气电池具有1.48 V的高开路电压和52.6 mW cm−2的最大功率密度，显示出迷人的商业前景。
Due to the limited sources, high cost, and poor long-term stability of noble metal catalysts, the large-scale commercial application of zinc-air batteries has been restricted. Therefore, designing non-noble metal catalysts with excellent activity and stability for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) blossoms in the ascendant. Herein, we report a hollow star-shaped dual-functional electrocatalyst with uniform and dispersed Fe3N/Fe nanoparticles derived from zeolitic imidazolate framework (ZIFs) by a simple sacrificial template strategy. This hollow structure has the characteristics of low density, thin shell, and high permeability, and its internal cavity not only provides additional three-phase interfaces to accelerate O2reduction and evolution but also promotes the diffusion of reactants onto the catalyst. By controlling the input amount of iron metal salt, the dispersion degree of FeNPcan be effectively adjusted, and the generated Fe3N introduces abundant Fe-NXactive sites. Density functional theory calculations show that the strong affinity between Fe3N and FeNPis favorable for promoting the oxygen intermediate reaction, achieving a job-synergistic catalytic effect and high reaction kinetics. The synthesized Fe3N/FeNP-N-C-3.3% exhibits excellent dual-functional activity for OER and ORR, with a high half-wave potential of 0.867 V for ORR (better than the commercial Pt/C of 0.82 V) and an overpotential of only 294 mV for OER at 10 mA cm−2. The rechargeable Zn-air battery prepared with Fe3N/FeNP-N-C-3.3% as an air cathode shows a long-term cycling performance of over 750 h and a maximum power density of 205 mW cm−2. The flexible Zn-air battery has a high open-circuit voltage of 1.48 V and a maximum power density of 52.6 mW cm−2, showing glamorous commercial prospects.