Abstract
Sluggish kinetics of Mg2+ intercalation and low working potential seriously hinder the development of highenergy- density magnesium-ion batteries (MIBs). Hence developing cathode materials with fast Mg2+ diffusion and high working voltage is a key to overcome the obstacles in MIBs. Herein, a tetragonal NaV2O2(PO4)2F/reduced graphene oxide (rGO) is proposed as an effective Mg2+ host for the first time. It exhibits the highest average discharge voltage (3.3 V vs. Mg2+/Mg), fast diffusion kinetics of Mg2+ with the average diffusivity of 2.99×10−10 cm2 s−1, and ultralong cycling stability (up to 9500 cycles). The Mg2+ storage mechanism of NaV2O2(PO4)2F/rGO is demonstrated as a single-phase (de) intercalation reaction by in situ X-ray diffraction (XRD) technology. Density functional theory (DFT) computations further reveal that Mg2+ ions tend to migrate along the a direction. X-ray absorption near edge structure (XANES) demonstrates a decrease in the average valence of vanadium, and the local coordination environment around vanadium site is highly conserved after magnesiation. Moreover, the assembled NaV2O2(PO4)2F//Mg0.79NaTi2(PO4)3 Mg-ion full cell exhibits high power and energy densities, which indicates that NaV2O2(PO4)2F/rGO owns potential for practical applications. This work achieves a breakthrough in the working voltage of cathode materials for MIBs and provides a new opportunity for high-energy-density MIBs.
摘要
缓慢的Mg2+扩散动力学和低的工作电势严重阻碍高能量密度镁离子电池(MIBs)的发展. 因此, 开发具有快速Mg2+扩散和高工作电势的正极材料是克服MIBs发展阻碍的关键. 在本文中, 首次提出四方相的NaV2O2(PO4)2F/rGO作为一个有效的Mg2+宿主. 它展现出3.3 V vs. Mg2+/Mg的最高平均放电电压, 2.99×10−10 cm2 s−1的平均Mg2+扩散系数和9500个循环的超长循环寿命. 原位X射线衍射(XRD)表明NaV2O2(PO4)2F/rGO的储镁机制为单相的嵌入/脱出反应. 密度泛函理论(DFT)计算表明Mg2+倾向于沿a方向迁移. X射线吸收近边结构(XANES)表明镁化后钒的平均价态降低且钒位点周围的配位环境得到高度保持. 此外, 组装的NaV2O2(PO4)2F//Mg0.79NaTi2(PO4)3镁离子全电池表现出高的功率和能量密度, 表明NaV2O2(PO4)2F/rGO具有实际应用的潜力. 本工作在MIBs正极材料的工作电压方面实现了突破并为发展高能量密度的MIBs提供了新的机会.
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Acknowledgements
This work was supported by the National Key Research and Development Program of China (2016YFA0202603 and 2016YFA0202601), the National Natural Science Fund for Distinguished Young Scholars (51425204), the National Natural Science Foundation of China (51832004, 51602239 and 51672307), and the International Science & Technology Cooperation Program of China (2013DFA50840).
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Author contributions Mai L, An Q and Wang J conceived the study. Tan S and Wang J performed the electrochemical measurements together with Huang D and Zhang G conducted the Rietveld refinement. Jiang Y performed the first-principles calculations. Yin Y designed the synthesis method. Zhang G and Li Q performed the V K-edge experiments. Zhang Q and Gu L conducted the TEM measurements and analysis. Wang J, Tan S, An Q and Xiong F participated in the all data analysis and wrote the manuscript together with Mai L. Mai L and An Q provided insights for the experiments and supervised the research. All authors agreed with the final version of the manuscript.
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Junjun Wang received his BS degree in materials science and engineering from Henan Polytechnic University in 2017. He is currently working toward the master’s degree in materials science and engineering at Wuhan University of Technology (WUT). His current research focuses on rechargeable magnesium and calcium batteries.
Shuangshuang Tan received his BS degree in materials science and engineering from WUT in 2016. He is currently working toward the PhD degree at WUT and his current research focuses on rechargeable magnesium batteries and metalsulfur batteries.
Qinyou An is an associate professor of materials science and engineering at WUT. He received his PhD degree from WUT in 2014. He carried out his postdoctoral research in the laboratory of Prof. Yan Yao at the University of Houston in 2014–2015. Currently, his research interest includes energy-storage materials and devices.
Liqiang Mai is Changjiang Scholar Chair Professor of materials science and engineering at WUT. He is the winner of the National Natural Science Fund for Distinguished Young Scholars and Fellow of the Royal Society of Chemistry. He received his PhD from WUT in 2004 and carried out his postdoctoral research with Prof. Zhong Lin Wang at Georgia Institute of Technology in 2006–2007. He worked as an advanced research scholar with Prof. Charles M. Lieber at Harvard University in 2008–2011 and Prof. Peidong Yang at University of California, Berkeley in 2017. His current research interests focus on new nanomaterials for electrochemical energy storage and micro/nano energy devices.
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Wang, J., Tan, S., Zhang, G. et al. Fast and stable Mg2+ intercalation in a high voltage NaV2O2(PO4)2F/rGO cathode material for magnesium-ion batteries. Sci. China Mater. 63, 1651–1662 (2020). https://doi.org/10.1007/s40843-020-1311-1
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DOI: https://doi.org/10.1007/s40843-020-1311-1