Efficiently boosting oxygen reduction activity of MnO2 with tailored surface oxygen vacancies by ball milling

doi:10.1016/j.cjche.2025.05.039

中国化学工程学报 ›› 2025, Vol. 87 ›› Issue (11): 58-65.DOI: 10.1016/j.cjche.2025.05.039

Efficiently boosting oxygen reduction activity of MnO₂ with tailored surface oxygen vacancies by ball milling

Danlin Wang¹, Jiajin Luo¹, Junning Li¹, Yuyang Zheng¹, Yajing Su¹, Zhuoli Deng¹, Gao Cheng^1,2, Yingying Xu¹, Ying Wu^1,2,3, Yuanhong Zhong^1,2, Ming Sun^1,2, Lin Yu^1,2

1. School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China;
2. Jieyang Branch of Chemistry and Chemical Engineering Guangdong Laboratory, Rongjiang Laboratory, Jieyang 515200, China;
3. School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641, China

收稿日期:2025-03-10 修回日期:2025-05-26 接受日期:2025-05-29 出版日期:2025-11-28 发布日期:2025-08-05
通讯作者: Gao Cheng,E-mail:chengg36@gdut.edu.cn;Ming Sun,E-mail:hukis@126.com;Lin Yu,E-mail:gych@gdut.edu.cn
基金资助:
This work is financially supported by the Science and Technology Program of Guangzhou (202201010373).

Efficiently boosting oxygen reduction activity of MnO₂ with tailored surface oxygen vacancies by ball milling

Danlin Wang¹, Jiajin Luo¹, Junning Li¹, Yuyang Zheng¹, Yajing Su¹, Zhuoli Deng¹, Gao Cheng^1,2, Yingying Xu¹, Ying Wu^1,2,3, Yuanhong Zhong^1,2, Ming Sun^1,2, Lin Yu^1,2

1. School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China;
2. Jieyang Branch of Chemistry and Chemical Engineering Guangdong Laboratory, Rongjiang Laboratory, Jieyang 515200, China;
3. School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641, China

Received:2025-03-10 Revised:2025-05-26 Accepted:2025-05-29 Online:2025-11-28 Published:2025-08-05
Contact: Gao Cheng,E-mail:chengg36@gdut.edu.cn;Ming Sun,E-mail:hukis@126.com;Lin Yu,E-mail:gych@gdut.edu.cn
Supported by:
This work is financially supported by the Science and Technology Program of Guangzhou (202201010373).

摘要/Abstract

摘要： Oxygen vacancy engineering is a valid strategy to boost the oxygen reduction reaction (ORR) performance of nanostructured electrocatalysts. Current methods for generating surface oxygen vacancies (V_os) in nanostructured MnO₂ is mostly lab-scale, which cannot meet the requirement of large-scale production. Herein, we employed a mechanochemical method of ball milling to introduce surface V_os into the β-MnO₂ nanoparticles. The ball milling process generated abundant surface V_os, which significantly facilitated the adsorption and activation of O₂. Consequently, the ORR performance of ball-milled β-MnO₂ was markedly boosted by varying the ball milling time. As an air cathode catalyst for zinc-air battery (ZAB), the β-MnO₂ ball-milled for 4 h displayed a high specific capacity of 804 mA·h·g^-1 and excellent cycling over 500 h at 5 mA·cm^-2, which were superior than those of pristine β-MnO₂-based ZAB. Our work offers a feasible strategy to enhance electrocatalytic ORR performance of MnO₂, which shows significant potential for large-scale production of efficient ORR electrocatalysts.

关键词: MnO₂ catalysts, Ball milling, Oxygen vacancy, Electrochemistry, Oxygen reduction reaction, Zinc-air battery

Abstract: Oxygen vacancy engineering is a valid strategy to boost the oxygen reduction reaction (ORR) performance of nanostructured electrocatalysts. Current methods for generating surface oxygen vacancies (V_os) in nanostructured MnO₂ is mostly lab-scale, which cannot meet the requirement of large-scale production. Herein, we employed a mechanochemical method of ball milling to introduce surface V_os into the β-MnO₂ nanoparticles. The ball milling process generated abundant surface V_os, which significantly facilitated the adsorption and activation of O₂. Consequently, the ORR performance of ball-milled β-MnO₂ was markedly boosted by varying the ball milling time. As an air cathode catalyst for zinc-air battery (ZAB), the β-MnO₂ ball-milled for 4 h displayed a high specific capacity of 804 mA·h·g^-1 and excellent cycling over 500 h at 5 mA·cm^-2, which were superior than those of pristine β-MnO₂-based ZAB. Our work offers a feasible strategy to enhance electrocatalytic ORR performance of MnO₂, which shows significant potential for large-scale production of efficient ORR electrocatalysts.

Key words: MnO₂ catalysts, Ball milling, Oxygen vacancy, Electrochemistry, Oxygen reduction reaction, Zinc-air battery

Danlin Wang, Jiajin Luo, Junning Li, Yuyang Zheng, Yajing Su, Zhuoli Deng, Gao Cheng, Yingying Xu, Ying Wu, Yuanhong Zhong, Ming Sun, Lin Yu. Efficiently boosting oxygen reduction activity of MnO₂ with tailored surface oxygen vacancies by ball milling[J]. 中国化学工程学报, 2025, 87(11): 58-65.

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Efficiently boosting oxygen reduction activity of MnO₂ with tailored surface oxygen vacancies by ball milling

Efficiently boosting oxygen reduction activity of MnO₂ with tailored surface oxygen vacancies by ball milling

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