NH4V4O10 层间空间的定量调节以实现快速和持久的 Zn2+ 和 NH4+ 存储,Advanced Science

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NH4V4O10 层间空间的定量调节以实现快速和持久的 Zn2+ 和 NH4+ 存储
Advanced Science ( IF 14.3 ) Pub Date : 2023-01-25 , DOI: 10.1002/advs.202206836
Shuyue Li _{1,

2} , Dongxu Yu _{1,

3} , Jingyi Liu ₁ , Nan Chen ₁ , Zexiang Shen ₄ , Gang Chen ₁ , Shiyu Yao ₁ , Fei Du ₁

Affiliation

层状钒基氧化物是用于水系锌离子电池（AZIB）的有前途的阴极材料。在此，提出了一种可以有效定量调节层状 NH ₄ V ₄ O ₁₀层间距的原位电化学策略，并揭示了最佳性能与层间距之间的密切关系。具体而言，通过将截止电压从 1.4、1.6 增加到 1.8 V，NH ₄ V ₄ O ₁₀的层间距可以得到很好的控制，分别扩大到 10.21、11.86 和 12.08 Å，远大于原始层间距（ 9.5 埃）。其中，正极充电至1.6 V (NH ₄ V ₄ O₁₀ -C1.6)，表现出最佳的 Zn ²⁺存储性能，包括10 A g -1 下^{223 mA hg}^-1的高容量和 1000 次循环后容量保持率为 97.5% 的长期稳定性。如此优异的性能可归因于活性氧化还原位点、电荷转移动力学和晶体结构稳定性之间的良好平衡，这是通过仔细控制层间空间实现的。此外，NH ₄ V ₄ O ₁₀ -C1.6 提供 NH ₄⁺存储性能，其容量在 0.1 A g ⁻¹时达到 296 mA hg ⁻¹并且寿命在 5 A g ^{−1下持续超过 3000 个循环}. 该研究为理解水介质中离子存储层间空间的局限性提供了新的见解，并指导了高性能正极材料的探索。

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Quantitative Regulation of Interlayer Space of NH4V4O10 for Fast and Durable Zn2+ and NH4+ Storage

Layered vanadium-based oxides are the promising cathode materials for aqueous zinc-ion batteries (AZIBs). Herein, an in situ electrochemical strategy that can effectively regulate the interlayer distance of layered NH₄V₄O₁₀ quantitatively is proposed and a close relationship between the optimal performances with interlayer space is revealed. Specifically, via increasing the cutoff voltage from 1.4, 1.6 to 1.8 V, the interlayer space of NH₄V₄O₁₀ can be well-controlled and enlarged to 10.21, 11.86, and 12.08 Å, respectively, much larger than the pristine one (9.5 Å). Among them, the cathode being charging to 1.6 V (NH₄V₄O₁₀-C1.6), demonstrates the best Zn²⁺ storage performances including high capacity of 223 mA h g⁻¹ at 10 A g⁻¹ and long-term stability with capacity retention of 97.5% over 1000 cycles. Such superior performances can be attributed to a good balance among active redox sites, charge transfer kinetics, and crystal structure stability, enabled by careful control of the interlayer space. Moreover, NH₄V₄O₁₀-C1.6 delivers NH₄⁺ storage performances whose capacity reaches 296 mA h g⁻¹ at 0.1 A g⁻¹ and lifespan lasts over 3000 cycles at 5 A g⁻¹. This study provides new insights into understand the limitation of interlayer space for ion storage in aqueous media and guides exploration of high-performance cathode materials.

更新日期：2023-01-25

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