高效的尖晶石铁钴氧/氮掺杂有序介孔碳催化剂应用于可充电锌-空气电池

doi:10.1016/S1872-2067(20)63752-4

催化学报 ›› 2021, Vol. 42 ›› Issue (9): 1451-1458.DOI: 10.1016/S1872-2067(20)63752-4

高效的尖晶石铁钴氧/氮掺杂有序介孔碳催化剂应用于可充电锌-空气电池

韦何磊^a, 谭爱东^a^,^*(), 胡树枝^a, 朴金花^b, 傅志勇^a^,^#()

^a华南理工大学化学与化工学院, 广东省燃料电池技术重点实验室, 广东广州510641
^b华南理工大学食品科学与工程学院, 广东广州510641

收稿日期:2020-11-25 接受日期:2020-12-22 出版日期:2021-09-18 发布日期:2021-05-16
通讯作者: 谭爱东,傅志勇
基金资助:
国家自然科学基金(21903026);国家自然科学基金(21975081);国家自然科学基金(21975079);博士后科学基金(2019M652877);中央高校基础研究基金

Efficient spinel iron-cobalt oxide/nitrogen-doped ordered mesoporous carbon catalyst for rechargeable zinc-air batteries

He-lei Wei^a, Ai-dong Tan^a^,^*(), Shu-zhi Hu^a, Jin-hua Piao^b, Zhi-yong Fu^a^,^#()

^aKey Laboratory on Fuel Cell Technology of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641, Guangdong, China
^bSchool of Food Science and Engineering, South China University of Technology, Guangzhou 510641, Guangdong, China

Received:2020-11-25 Accepted:2020-12-22 Online:2021-09-18 Published:2021-05-16
Contact: Ai-dong Tan,Zhi-yong Fu
About author:^# E-mail: zyfu@scut.edu.cn
^* Tel: +86-20-87113584; E-mail: tanad@scut.edu.cn;
Supported by:
National Natural Science Foundation of China(21903026);National Natural Science Foundation of China(21975081);National Natural Science Foundation of China(21975079);China Postdoctoral Science Foundation(2019M652877);Fundamental Research Funds for the Central Universities

摘要/Abstract

摘要：

以电催化为核心的新能源储存和转换技术为缓解能源与环境问题提供了有效手段. 可充电锌空气电池因其理论能量密度(1086 Wh·kg^‒1)高、成本效益显著、安全系数高、环境友好及放电平稳等优点被认为是一种具有前景的能源存储/转换装置, 有望在新能源汽车、便携式电源等领域广泛应用. 氧还原反应(ORR)和氧析出反应(OER)是锌-空气电池中的核心反应, 目前, 虽然贵金属催化剂对上述反应表现出一定的电催化活性, 但由于其稀缺性、高昂价格和低稳定性因素严重阻碍了它们在锌-空气电池中的广泛应用. 而非贵金属催化剂所面临的瓶颈在于ORR/OER反应动力学缓慢, 导致其在实际应用过程中存在电压效率低和催化剂腐蚀等问题. 因此, 为了推进锌-空气电池商业化进程, 研制低成本、高效、稳定的非贵金属催化剂迫在眉睫.
本文通过一步法将双金属前驱体嵌入氮掺杂有序介孔碳(NOMC)中, 合成了具有尖晶石型铁钴氧化物的高性能非贵金属电催化剂(Fe_xCo/NOMC, x代表铁钴的摩尔比). 实验结果表明, 在x = 0.5时, 所制备的催化剂具有最佳的催化活性, 与商业贵金属催化剂相比, 该催化剂展现更优的电催化活性和稳定性. 电化学测试结果表明, 其ORR的半波电位为0.89 V (vs. RHE), 当OER电流密度为10 mA·cm^‒1时, 过电势仅为0.31 V, 且电流-时间曲线测试结果表明催化剂表现出较好的稳定性. 通过X射线光电子能谱(XPS)、穆斯堡尔谱(Mössbauer)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和拉曼光谱(Raman)等表征手段对电催化剂的物化性质进行表征, 结果表明该材料优异的氧电催化性能归因于双金属氧化物的电子调控作用、NOMC的介孔结构、高导电性和高比表面积, 其ORR与OER的催化活性位点分别是氮活化的碳(N-C)和双金属氧化物. 以优化的Fe_0.5Co/NOMC为正极组装可充电锌-空气电池, 该电池在空气环境下展现出优良的充放电性能, 其在电流密度为100 mA·cm^‒2条件下操作时能量密度达到820 Wh·kg^‒1, 在1.0 V时功率密度达到153 mW·cm^‒2, 它还表现出较好的稳定性, 经过144 h的循环实验, 活性没有明显下降. 本文不仅制备了一种有前景的尖晶石型氧化物碳基氧电催化材料, 还为高效氧电催化剂的合理开发与构筑提供了一条新的思路.

Abstract:

A robust oxygen-related electrocatalyst, composed of spinel iron-cobalt oxide and nitrogen-doped ordered mesoporous carbon (NOMC), was developed for rechargeable metal-air batteries. Electrochemical tests revealed that the optimal catalyst Fe_0.5Co/NOMC exhibits superior activity with a half-wave potential of 0.89 V (vs. reversible hydrogen electrode) for the oxygen reduction reaction and an overpotential of 0.31 V at 10 mA cm^-2 for the oxygen evolution reaction. For demonstration, the catalyst was used in the assembly of a rechargeable zinc-air battery, which exhibited an exceptionally high energy density of 820 Wh kg^-1 at 100 mA cm^-2, a high power density of 153 mW cm^-2at 1.0 V, and superior cycling stability up to 432 cycles (144 h) under ambient air.

Key words: Oxygen-related catalyst, Oxygen evolution reaction, Oxygen reduction reaction, Spinel oxide, Zinc-air battery

韦何磊, 谭爱东, 胡树枝, 朴金花, 傅志勇. 高效的尖晶石铁钴氧/氮掺杂有序介孔碳催化剂应用于可充电锌-空气电池[J]. 催化学报, 2021, 42(9): 1451-1458.

He-lei Wei, Ai-dong Tan, Shu-zhi Hu, Jin-hua Piao, Zhi-yong Fu. Efficient spinel iron-cobalt oxide/nitrogen-doped ordered mesoporous carbon catalyst for rechargeable zinc-air batteries[J]. Chinese Journal of Catalysis, 2021, 42(9): 1451-1458.

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图/表 8

Fig. 1. (a) Schematic illustration of the synthesis protocol of FexCo/NOMC; (b) Nitrogen ad/de-sorption isotherms and (c) XRD patterns of all the samples; (d) M?ssbauer spectroscopy of Fe0.5Co/NOMC.

Fig. 2. (a) TEM image and b) corresponding particle size distribution diagram of Fe0.5Co/NOMC; (c) Size distribution of all the samples; (d?f) Elemental mapping images of Fe0.5Co/NOMC.

Fig. 3. XPS survey spectra of Fe/NOMC, Fe2Co/NOMC, FeCo/NOMC, Fe0.5Co/NOMC and Co/NOMC.

Fig. 4. High-resolution XPS spectra of Fe 2p peak and peak fitting result of (a) Fe/NOMC, (b) Fe2Co/NOMC, (c) FeCo/NOMC, (d) Fe0.5Co/NOMC.

Fig. 5. High-resolution XPS spectra of Co 2p peak and peak fitting result of (a) Fe2Co/NOMC, (b) FeCo/NOMC, (c) Fe0.5Co/NOMC, (d) Co/NOMC.

Table 1 Elemental composition (at. %) measured by XPS.

Sample	C	N	O	Fe	Co	Fe:Co
Fe/NOMC	81.14	1.75	15.25	1.86	0	—
Fe₂Co/NOMC	82.42	1.76	13.16	1.72	0.94	1.83
FeCo/NOMC	83.36	1.79	12.52	1.08	1.25	0.78
Fe_0.5Co/NOMC	82.41	1.82	13.39	0.82	1.56	0.53
Co/NOMC	81.01	1.50	15.76	0	1.73	—

Fig. 6. (a) ORR’s polarization curves (scanning rate: 10 mV s-1, rotating rate: 1600 rpm, O2-saturated 0.10 M KOH solution), (b) the corresponding current density at 0.90 V, and (c) electron transfer number (n) of all the catalysts; (d) OER’s polarization curves (scanning rate: 5 mV s-1, rotating rate: 1600 rpm, O2-saturated 1.0 M KOH solution), and (e) OER’s overpotential at 10 mA cm-2 of all the catalysts; (f) Full-potential-window polarization curve of Fe0.5Co/NOMC.

Fig. 7. (a) Discharging and charging polarization curves, and (b) power density diagram of Zn-air battery assembled with Fe0.5Co/NOMC and IrO2+Pt/C, respectively; (c) Specific capacity and (d) specific energy density diagrams at 100 mA cm?2, and (e) cycling performance at 5 mA cm?2 for 10 min discharging and 10 min charging of Zn-air battery assembled with Fe0.5Co/NOMC; (f) Schematic of the rechargeable Zn-air battery; (g) Photo of thirty-eight LEDs powered by two rechargeable Zn-air batteries Photo of 38 LEDs powered by two rechargeable Zn-air batteries.

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高效的尖晶石铁钴氧/氮掺杂有序介孔碳催化剂应用于可充电锌-空气电池

Efficient spinel iron-cobalt oxide/nitrogen-doped ordered mesoporous carbon catalyst for rechargeable zinc-air batteries

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