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多钒氧酸盐K9PV14O42的合成及其储锌性能的研究
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Abstract:
水系锌离子电池(AZIBs)正极材料受限于Zn2+扩散动力学缓慢和循环稳定性差，开发新型高性能正极材料是推动AZIBs走向实用的核心任务。本研究以Keggin型多钒氧酸盐K9PV14O42为研究对象，利用团簇间丰富的通道和空隙实现Zn2+的传输与存储，并通过K+作为抗衡阳离子在充放电过程中的部分离子交换，起到稳定结构和辅助电导的作用。XRD和FTIR证实材料成功合成，TG显示其热稳定性良好，SEM表明其形貌可为Zn2+的嵌入提供丰富的活性位点。电化学测试表明，K9PV14O42具有良好的比容量和循环稳定性：在0.1 mV？s？1扫描速率下，前四圈CV曲线逐步趋于重合，显示良好的可逆性；在0.1 A？g？1电流密度下循环100圈时比容量为162.5 mAh？g？1，在1 A？g？1下循环400圈仍保持101.7 mAh？g？1，库伦效率始终接近100%；不同电流密度下的倍率测试及前三圈GCD结果均与CV结论一致。本工作为构建高容量、结构稳定的钒基正极材料提供了新思路，丰富了多钒氧酸盐在AZIBs领域的应用研究。
Cathode materials for aqueous zinc-ion batteries (AZIBs) are severely constrained by sluggish Zn2+ diffusion kinetics and poor cycling stability, which arise from the strong electrostatic interactions between the divalent Zn2+ ions and the anionic frameworks of host materials. Developing novel high-performance cathode materials with open frameworks and robust structural stability is therefore a core task for promoting the practical application of AZIBs. Polyoxovanadates (POVs), as a subclass of polyoxometalates, feature well-defined cluster structures, tunable compositions, and abundant inter-cluster voids, making them promising candidates for multivalent ion storage. In this study, the Keggin-type polyoxovanadate K9PV14O42 is investigated as a cathode material for AZIBs, aiming to achieve high reversible capacity and long-term cycling stability through its unique structural advantages. The K9PV14O42 material was synthesized via a straightforward aqueous solution method. Structural characterization confirmed the successful synthesis of phase-pure K9PV14O42 with a well-defined Keggin-type architecture. XRD patterns showed sharp and distinct diffraction peaks matching the standard PDF card, with no detectable impurity peaks, indicating high crystallinity and long-range structural order. FTIR spectra revealed characteristic absorption bands at 950 cm？1 (terminal V=O stretching), 850 and 790 cm？1 (asymmetric V-O-V or V-O-P bridging vibrations), and 1050 cm？1 (P-O vibration of the central PO4 tetrahedron), which
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