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Constructing highly safe and long-life calcium ion batteries based on hydratedvanadium oxide cathodes featuring a pillar structure

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Abstract

Calcium-ion batteries (CIBs) have generated intense interest due to the growing demand for safer, cheaper, and large-scale energy storage systems. However, their development is still in its infancy, owing to the lack of suitable cathodes for sustaining reversible Ca2+ intercalation/deintercalation. Herein, layered H2V3O8 (HVO) with Zn2+ pre-insertion (ZHVO) is reported as a high-rate and highly durable cathode material for CIBs. The existence of Zn2+ and H2O pillars could expand the interlayer spacing up to 1.8 nm, which is favorable for the diffusion of bulky Ca2+. The formation of Zn–O bonds facilitates electron transfer and enhances electrical conduction. Consequently, the ZHVO cathode achieves superior capacity performance (213.9 mAh·g−1 at 0.2 A·g−1) and long lifespan (78.3% for 1,000 cycles at 5 A·g−1) compared to pristine HVO. Density functional theory (DFT) calculations revealed that Zn2+ moved during Ca2+ intercalation, thereby reducing the diffusion energy barrier and facilitating Ca2+ diffusion. Finally, a safe aqueous calcium ion cell was successfully assembled.

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摘要 (Chinese abstract)

由于对更安全、更廉价的大规模储能系统的需求日益增长, 钙离子电池 (CIBs) 引起了人们的浓厚兴趣。然而, 由于缺乏合适的阴极来维持 Ca2+ 的可逆嵌入/脱出, 钙离子电池的发展仍处于起步阶段。在此, 研究人员报告了预嵌 Zn2+ 的层状 H2V3O8 (ZHVO), 它是一种用于 CIB 的高速率、高耐久性阴极材料。Zn2+ 和 H2O 支柱的存在可将层间距扩大到 1.8 nm, 有利于大半径 Ca2+ 的扩散。另外, Zn–O 键的形成促进了电子转移并增强了导电性。因此, 与原始 HVO 相比, ZHVO 阴极实现了更高的比容量 (213.9 mAh·g−1 @ 0.2 A·g−1) 和更长的寿命 (78.3% for 1000 cycles @ 5 A·g−1) 。DFT 计算显示, Zn2+ 在 Ca2+ 嵌入过程中移动, 降低了扩散能垒, 促进了 Ca2+ 扩散。最后, 使用ZHVO作为阴极材料成功组装了一个高度安全的全水钙离子电池。

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Acknowledgements

This study was financially supported by the Open Research Found of Songshan Lake Materials Laboratory (No. 2021SLABFN04), National Natural Science Foundation of China (Nos. 22109134 and 52171025), Guangdong Basic and Applied Basic Research Foundation (No. 2022A1515010920), the Outstanding Youth Basic Research Project of Shenzhen (No. RCYX20221008092934093). The High-Performance Computing Center of Central South University assists with the computation parts. The TEM work used the resources of the Analyses and Testing Center at the Dongguan University of Technology.

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  1. Powder Metallurgy Research Institute, Central South University, Changsha, 410083, China

    Chun-Fang Wang, Shi-Wei Zhang, Lan Huang, Feng Liu, Jian-Chuan Wang & Li-Ming Tan

  2. Research Institute of Interdisciplinary Science and School of Materials Science and Engineering, Dongguan University of Technology, Dongguan, 523808, China

    Yuan-Min Zhu

  3. Songshan Lake Materials Laboratory, Dongguan, 523808, China

    Chun-Fang Wang & Chun-Yi Zhi

  4. Department of Materials Science and Engineering, City University of Hong Kong, Hong Kong, 999077, China

    Chun-Yi Zhi

  5. Faculty of Materials Science and Energy Engineering/Institute of Technology for Carbon Neutrality, Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen, 518055, China

    Cui-Ping Han

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Wang, CF., Zhang, SW., Huang, L. et al. Constructing highly safe and long-life calcium ion batteries based on hydratedvanadium oxide cathodes featuring a pillar structure. Rare Met. 43, 2597–2612 (2024). https://doi.org/10.1007/s12598-023-02613-5

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