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研究论文

Mn掺杂Co3O4双功能电催化剂在碱性介质下氧还原和析氧反应中的应用

税子怡a,b, 于思乐c, 陆伟a, 许留云b, 刘庆叶a, 赵炜*,a, 刘益伦d   

  1. a西北大学 化工学院 西安 710069;
    b延安大学 化学与化工学院 延安 716000;
    c比亚迪汽车有限公司 西安 710075;
    d西安交通大学 航空航天学院 西安 710049
  • 投稿日期:2024-05-06
  • 基金资助:
    陕西省自然科学基础研究计划资助（2023-JC-YB-046）和陕西省教育厅自然科学基金（23JK0723）.

Bifunctional electrocatalysts of Mn-doped Co3O4 for oxygen reduction and oxygen evolution reactions in alkaline medium

Ziyi Shuia,b, Sile Yuc, Wei Lua, Liuyun Xub, Qingye Liua, Wei Zhao*,a, Yilun Liud   

  1. aNorthwest University, School of Chemical Engineering, Xi’an, 710069;
    bCollege of Chemistry & Chemical Engineering, Yan’an University, Yan’an 716000;
    cBYD Automobile Co., Ltd. Xi’an, 710075;
    dSchool of Aerospace, Xi’an Jiao tong University, Xi’an 710049
  • Received:2024-05-06
  • Contact: * E-mail: zhaowei3313@nwu.edu.cn

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可充锌空气电池（ZABs）由于其高能量和功率密度、高安全性和成本效益,被认为是未来储能领域中最有前途的清洁电源之一。然而,其实际应用受到放电和充电过程中氧还原反应（ORR）和析氧反应（OER）动力学缓慢的阻碍。Pt和IrO2是目前公认的高效ORR和OER催化剂,但贵金属催化剂的高成本阻碍了它们商业化的步伐。本文通过共沉淀法制备了一系列尖晶石催化剂（Mnx-Co3O4,x=0, 0.5, 1, 1.5）,以实现在碱性介质中高效催化ORR和OER的目的,并进一步探索这些过渡金属氧化物催化材料作为双功能复合催化剂在取代贵金属方面的潜力。实验结果显示：Mn-Co3O4具有优异的ORR性能（起始电位为0.85 V,半波电位为0.69 V）和OER性能（过电位为0.57 V,电子转移电阻为26.14 Ω）。此外,密度泛函理论（DFT）计算表明,Mn和Co位点可以分别作为ORR和OER的潜在活性位点,在电催化过程中具有显著的协同作用。表征结果进一步证实锰的掺杂增加了催化剂的比表面积和氧空位,调整了催化剂表面化学和电子状态,从而提高了催化剂的ORR和OER性能。另外,该催化剂在液态可充电锌空气电池在中显示出长达40 h的循环寿命。总而言之,本文证明了锰钴双金属协同催化是提高ORR和OER选择性的一种有效策略。

关键词: 氧还原反应, 析氧反应, 尖晶石氧化物, 氧空位, 催化性能

Rechargeable zinc-air batteries (ZABs) have been extensively studied due to their due to their high energy and power density, high safety and cost-effectiveness, which are considered to be one of the most promising clean power sources in the field of energy storage. Nevertheless, its practical application has been hampered by the sluggish kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) during the discharge and charge processes, respectively. It is well known that Pt and IrO2 are currently considered to be the most efficient ORR and OER catalysts. However, the high cost of precious metal catalysts has hindered their large-scale application. Herein, a series of spinel catalysts (Mnx-Co3O4, x=0, 0.5, 1, 1.5) are prepared by co-precipitation method to achieve bifunctional oxygen electrocatalysis in alkaline media. Meanwhile, the potential of these transition metal oxide catalytic materials as bifunctional catalysts in replacing precious metals has been further explored. The results show that Mn-Co3O4 has excellent ORR performance (onset potential of 0.85 V, half-wave potential of 0.69 V), and significantly enhanced OER performance (overpotential of 0.57 V, the electron transfer resistance of 26.14 Ω), thereby leading to excellent bifunctional property. Furthermore, Density functional theory (DFT) calculations demonstrate that Mn and Co sites can serve as potential active sites for ORR and OER respectively, exhibiting significant synergistic effects in electrocatalytic processes. The characterization results further confirm that the doping of manganese in the catalyst preparation process increases the specific surface area and oxygen vacancies of the catalyst, adjusts the surface chemistry and electronic state of the catalyst, and thus improves the ORR and OER performance of the catalyst. In addition, the catalyst delivers high cycle life of up to 40 h in liquid rechargeable zinc air batteries. In summary, this paper demonstrates that manganese-cobalt bimetallic synergistic catalysis is a promising strategy to enhance the electrocatalytic activity of ORR and OER.

Key words: Oxygen reduction reaction, Oxygen evolution reaction, Spinel oxide, Oxygen vacancy, Catalytic performance