Efficient Regulation of Oxygen Vacancies in β-MnO<sub>2</sub> Nanostructures for High-Loading Zinc-Ion Batteries
Manganese-based oxides, particularly β-MnO<sub>2</sub>, have emerged as promising cathode materials for aqueous zinc-ion batteries (ZIBs) due to their high theoretical capacity, low cost, and intrinsic safety. However, their sluggish reaction kinetics, limited active sites, and poor cond...
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MDPI AG
2025-05-01
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| Online Access: | https://www.mdpi.com/2075-4701/15/5/526 |
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| author | Jian-Chun Wu Yaoyu Yin Haitao Zhou Xicheng Shen Hongquan Gao Xiaowei Li Zhiyong Liu Yihong Deng Yanxin Qiao |
| author_facet | Jian-Chun Wu Yaoyu Yin Haitao Zhou Xicheng Shen Hongquan Gao Xiaowei Li Zhiyong Liu Yihong Deng Yanxin Qiao |
| author_sort | Jian-Chun Wu |
| collection | DOAJ |
| description | Manganese-based oxides, particularly β-MnO<sub>2</sub>, have emerged as promising cathode materials for aqueous zinc-ion batteries (ZIBs) due to their high theoretical capacity, low cost, and intrinsic safety. However, their sluggish reaction kinetics, limited active sites, and poor conductivity often lead to suboptimal electrochemical performance. To address these limitations, we propose a facile ethanol-mediated hydrothermal strategy to engineer rod-like β-MnO<sub>2</sub> nanostructures with tailored oxygen vacancies. By precisely adjusting ethanol addition (3–5 mL) during synthesis, oxygen vacancy concentrations were optimized to enhance electronic conductivity and active site exposure. The experimental results demonstrate that β-MnOx-2-5 synthesized with 5 mL of ethanol delivers an exceptional areal capacity of 4.87 mAh cm<sup>−2</sup> (348 mAh g<sup>−1</sup>, 469.8 Wh kg<sup>−1</sup>) at 200 mA cm<sup>−2</sup> under a high mass loading of 14 mg cm<sup>−2</sup>. Further, a hybrid electrode combining oxygen-deficient β-MnO<sub>2</sub>-x-3 (air-calcined) and structurally stable β-Mn<sub>5</sub>O<sub>8</sub>-y-3 (Ar-calcined) achieves a retained capacity of 3.9 mAh cm<sup>−2</sup> with stable cycling performance, achieving an optimal equilibrium between high capacity and long-term operational durability. Systematic characterizations (XPS, ESR, XANES, FT-EXAFS) confirm vacancy-induced electronic structure modulation, accelerating ion diffusion and redox kinetics. This scalable vacancy engineering approach, requiring only ethanol dosage control, presents a viable pathway toward industrial-scale ZIB applications. |
| format | Article |
| id | doaj-art-d3d6ecc18f534e4ba3cc3bdde2d3fef0 |
| institution | Kabale University |
| issn | 2075-4701 |
| language | English |
| publishDate | 2025-05-01 |
| publisher | MDPI AG |
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| series | Metals |
| spelling | doaj-art-d3d6ecc18f534e4ba3cc3bdde2d3fef02025-08-20T03:47:58ZengMDPI AGMetals2075-47012025-05-0115552610.3390/met15050526Efficient Regulation of Oxygen Vacancies in β-MnO<sub>2</sub> Nanostructures for High-Loading Zinc-Ion BatteriesJian-Chun Wu0Yaoyu Yin1Haitao Zhou2Xicheng Shen3Hongquan Gao4Xiaowei Li5Zhiyong Liu6Yihong Deng7Yanxin Qiao8School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, ChinaSchool of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, ChinaSchool of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, ChinaSchool of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, ChinaSchool of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, ChinaSchool of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, ChinaSchool of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, ChinaSchool of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, ChinaSchool of Materials Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, ChinaManganese-based oxides, particularly β-MnO<sub>2</sub>, have emerged as promising cathode materials for aqueous zinc-ion batteries (ZIBs) due to their high theoretical capacity, low cost, and intrinsic safety. However, their sluggish reaction kinetics, limited active sites, and poor conductivity often lead to suboptimal electrochemical performance. To address these limitations, we propose a facile ethanol-mediated hydrothermal strategy to engineer rod-like β-MnO<sub>2</sub> nanostructures with tailored oxygen vacancies. By precisely adjusting ethanol addition (3–5 mL) during synthesis, oxygen vacancy concentrations were optimized to enhance electronic conductivity and active site exposure. The experimental results demonstrate that β-MnOx-2-5 synthesized with 5 mL of ethanol delivers an exceptional areal capacity of 4.87 mAh cm<sup>−2</sup> (348 mAh g<sup>−1</sup>, 469.8 Wh kg<sup>−1</sup>) at 200 mA cm<sup>−2</sup> under a high mass loading of 14 mg cm<sup>−2</sup>. Further, a hybrid electrode combining oxygen-deficient β-MnO<sub>2</sub>-x-3 (air-calcined) and structurally stable β-Mn<sub>5</sub>O<sub>8</sub>-y-3 (Ar-calcined) achieves a retained capacity of 3.9 mAh cm<sup>−2</sup> with stable cycling performance, achieving an optimal equilibrium between high capacity and long-term operational durability. Systematic characterizations (XPS, ESR, XANES, FT-EXAFS) confirm vacancy-induced electronic structure modulation, accelerating ion diffusion and redox kinetics. This scalable vacancy engineering approach, requiring only ethanol dosage control, presents a viable pathway toward industrial-scale ZIB applications.https://www.mdpi.com/2075-4701/15/5/526zinc-ion batterycathodeoxygen vacancyhigh areal capacity |
| spellingShingle | Jian-Chun Wu Yaoyu Yin Haitao Zhou Xicheng Shen Hongquan Gao Xiaowei Li Zhiyong Liu Yihong Deng Yanxin Qiao Efficient Regulation of Oxygen Vacancies in β-MnO<sub>2</sub> Nanostructures for High-Loading Zinc-Ion Batteries Metals zinc-ion battery cathode oxygen vacancy high areal capacity |
| title | Efficient Regulation of Oxygen Vacancies in β-MnO<sub>2</sub> Nanostructures for High-Loading Zinc-Ion Batteries |
| title_full | Efficient Regulation of Oxygen Vacancies in β-MnO<sub>2</sub> Nanostructures for High-Loading Zinc-Ion Batteries |
| title_fullStr | Efficient Regulation of Oxygen Vacancies in β-MnO<sub>2</sub> Nanostructures for High-Loading Zinc-Ion Batteries |
| title_full_unstemmed | Efficient Regulation of Oxygen Vacancies in β-MnO<sub>2</sub> Nanostructures for High-Loading Zinc-Ion Batteries |
| title_short | Efficient Regulation of Oxygen Vacancies in β-MnO<sub>2</sub> Nanostructures for High-Loading Zinc-Ion Batteries |
| title_sort | efficient regulation of oxygen vacancies in β mno sub 2 sub nanostructures for high loading zinc ion batteries |
| topic | zinc-ion battery cathode oxygen vacancy high areal capacity |
| url | https://www.mdpi.com/2075-4701/15/5/526 |
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