钠离子电池正极材料Na2MnPO4F的23Na MAS NMR谱研究

doi:10.13208/j.electrochem.140401

电化学（中英文） ›› 2014, Vol. 20 ›› Issue (3): 201-205. doi: 10.13208/j.electrochem.140401

钠离子电池正极材料Na₂MnPO₄F的²³Na MAS NMR谱研究

侯旭，钟贵明，林晓琛，刘子庚，吴晓彪，杨勇^*

厦门大学化学化工学院化学系，固体表面物理化学国家重点实验室，福建厦门 361005

收稿日期:2014-04-01 修回日期:2014-04-14 出版日期:2014-06-28 发布日期:2014-04-21
通讯作者: 杨勇 E-mail:yyang@xmu.edu.cn
基金资助:
973国家重点基础研究发展计划（No. 2011CB935903）和国家自然科学基金（No. 21233004、No. 21021002）项目资助

²³Na MAS NMR Spectroscopic Study of Na₂MnPO₄F as Cathode Material for Sodium-Ion Battery

HOU Xu, ZHONG Gui-ming, LIN Xiao-chen, LIU Zi-geng, WU Xiao-biao, YANG Yong^*

State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China

Received:2014-04-01 Revised:2014-04-14 Published:2014-06-28 Online:2014-04-21
Contact: YANG Yong E-mail:yyang@xmu.edu.cn

摘要/Abstract

摘要： Na₂MnPO₄F材料是一种很有发展前景的钠离子电池正极材料，本文通过非原位XRD和固体核磁共振技术研究该材料充放电结构变化（晶体结构与局域Na位）. 非原位XRD测试发现，充电过程在2θ为31^o和36^o左右出现新的衍射峰，表明钠脱出后电极上有中间相物质生成. ²³Na MAS NMR谱图的-209 ppm、-258 ppm和-295 ppm三个谱峰分别对应于该材料结构中Na1 + Na2位、Na3位和Na4位. 非原位²³Na MAS NMR谱研究发现，充电过程中-209 ppm处信号峰面积比例减小，表明Na1和Na2位的Na比Na3和Na4位先脱出. 充电至4.2 V，-132 ppm和-330 ppm处出现中间相物质的信号峰；而放电过程则相反.

关键词: 钠离子电池, 正极材料, Na₂MnPO₄F, ²³Na MAS NMR

Abstract: The Na₂MnPO₄F is one of the promising cathode materials for the sodium ion batteries. In the paper, we employed the ex situ X-ray diffraction and solid state NMR techniques to study the charge and discharge processes of this material, including the crystal structure and sodium sites changes. The ex situ x-ray diffraction patterns showed that two new diffraction peaks could be observed at 31^o and 36^o indicating an intermediate phase formed with the extraction of Na+. From the ²³Na MAS NMR spectrum of the material, three peaks were seen at -209 ppm，-258 ppm and -295 ppm, which can be assigned to Na1 + Na2, Na3 and Na4 sites in the crystal structure, respectively. The ex situ solid state NMR study demonstrated that the Na+ in Na1 and Na2 sites deintercalated firstly compared to Na3 and Na4 sites. The signal peaks of intermediate phase appeared at -132 ppm and -330 ppm when charging to 4.2 V. The opposite phenomenon occurred during the discharge process.

Key words: sodium ion batteries, cathode material, Na₂MnPO₄F, ²³Na MAS NMR

中图分类号:

O646

侯旭，钟贵明，林晓琛，刘子庚，吴晓彪，杨勇*. 钠离子电池正极材料Na₂MnPO₄F的²³Na MAS NMR谱研究[J]. 电化学（中英文）, 2014, 20(3): 201-205.

HOU Xu, ZHONG Gui-ming, LIN Xiao-chen, LIU Zi-geng, WU Xiao-biao, YANG Yong*. ²³Na MAS NMR Spectroscopic Study of Na₂MnPO₄F as Cathode Material for Sodium-Ion Battery[J]. Journal of Electrochemistry, 2014, 20(3): 201-205.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.140401

https://electrochem.xmu.edu.cn/CN/Y2014/V20/I3/201

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钠离子电池正极材料Na₂MnPO₄F的²³Na MAS NMR谱研究

²³Na MAS NMR Spectroscopic Study of Na₂MnPO₄F as Cathode Material for Sodium-Ion Battery

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