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.

导出引用管理器 EndNote|Ris|BibTeX

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

参考文献

[1] Armand M, Tarascon J M. Building better batteries[J]. Nature, 2008, 451(7179): 652-657.
[2] Palomares V, Casas-Cabanas M, Castillo-Martinez E, et al. Update on Na-based battery materials. A growing research path[J]. Energy & Environmental Science, 2013, 6(8): 2312-2337.
[3] Pan H, Hu Y S, Chen L. Room-temperature stationary sodium-ion batteries for large-scale electric energy storage[J]. Energy & Environmental Science, 2013, 6(8): 2338-2360.
[4] Barpanda P, Chotard J N, Recham N, et al. Structural, transport, and electrochemical investigation of novel AMSO4F (A = Na, Li; M = Fe, Co, Ni, Mn) metal fluorosulphates prepared using low temperature synthesis routes[J]. Inorganic Chemistry, 2010, 49(16): 7401-7413.
[5] Hao X G (郝小罡), Liu Z G (刘子庚), Gong Z L (龚正良), et al. In situ XRD and solid state NMR characterization of Na3V2(PO4)2F3 as cathode material for lithium-ion batteries[J]. Scientia Sinica Chimica (中国科学：化学), 2012, 42(1): 38-46.
[6] Ellis B L, Makahnouk W R M, Makimura Y, et al. A multifunctional 3.5 V iron-based phosphate cathode for rechargeable batteries[J]. Nature Materials, 2007, 6(10): 749-753.
[7] Wu X, Zheng J, Gong Z, et al. Sol-gel synthesis and electrochemical properties of fluorophosphates Na2Fe1-xMnxPO4F/C (x = 0, 0.1, 0.3, 0.7, 1) composite as cathode materials for lithium ion battery[J]. Journal of Materials Chemistry, 2011, 21(46): 18630-18637.
[8] Kim S W, Seo D H, Kim H, et al. A comparative study on Na2MnPO4F and Li2MnPO4F for rechargeable battery cathodes[J]. Physical Chemistry Chemical Physics, 2012, 14(10): 3299-3303.
[9] Zhong Y J (钟艳君), Li J T (李君涛), Wu Z G (吴振国), et al. Synthesis of Na2MnPO4F/C with different carbon sources and their performances as cathode for lithium ion battery[J]. Acta Physico-Chimica Sinica (物理化学学报), 2013, 29(9): 1989-1997.
[11] Grey C P, Lee Y J. Lithium MAS NMR studies of cathode materials for lithium-ion batteries[J]. Solid State Sciences, 2003, 5(6): 883-894.
[10] Gong Z L, Yang Y. Recent advances in the research of polyanion-type cathode materials for Li-ion batteries[J]. Energy & Environmental Science, 2011, 4(9): 3223-3242.
[12] Zhong G M (钟贵明), Hou X (侯旭), Chen S S (陈守顺), et al. Solid-state NMR study of electrode/electrolyte materials for lithium ion batteries (in Chinese)[J]. Chinese Science Bulletin (科学通报), 2013, 58(32): 3287-3300.
[13] Jian Z, Yuan C, Han W, et al. Atomic structure and kinetics of NASICON NaxV2(PO4)3 cathode for sodium-ion batteries[J]. Advanced Functional Materials, 2014, doi: 10.1002/adfm.201400173.
[14] Davis L J M, Heinmaa I, Goward G R. Study of lithium dynamics in monoclinic Li3Fe2(PO4)3 using 6Li VT and 2D exchange MAS NMR spectroscopy[J]. Chemistry of Materials, 2009, 22(3): 769-775.
[15] Zheng Y, Zhang P, Wu S Q, et al. First-principles investigations on the Na2MnPO4F as a cathode material for Na-ion batteries[J]. Journal of the Electrochemical Society, 2013, 160(6): A927-A932.

Metrics

阅读次数

全文

1549

HTML			PDF

最新录用	在线预览	正式出版	最新录用	在线预览	正式出版
0	0	1	0	0	1548

来源	本网站	其他网站

次数	541	1008
比例	35%	65%

摘要

2418

最新录用	在线预览	正式出版

0	0	2418

来源	本网站	其他网站

次数	1065	1353
比例	44%	56%

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

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

Metrics

[1]	陈露露, 李浩冉, 刘维祎, 王伟. 锂离子电池正极材料原位漫反射光谱电化学研究[J]. 电化学（中英文）, 2024, 30(6): 2314006-.
[2]	殷秀平, 赵玉峰, 张久俊. 钠离子电池硬碳基负极材料的研究进展[J]. 电化学（中英文）, 2023, 29(10): 2204301-.
[3]	赵刚, 龚正良, 李益孝, 杨勇. 氧化钨和磷钨酸对LiNi_0.96Co_0.02Mn_0.02O₂材料的表面包覆改性研究[J]. 电化学（中英文）, 2023, 29(10): 2204281-.
[4]	胡炳文, 李超, 耿福山, 沈明. 金属离子电池中的磁共振：从核磁共振(NMR)到电子顺磁共振(EPR)[J]. 电化学（中英文）, 2022, 28(2): 2108421-.
[5]	骆晨旭, 师晨光, 余志远, 黄令, 孙世刚. 富锂锰基层状正极材料的合成及其首周过充下的结构演化[J]. 电化学（中英文）, 2022, 28(1): 2006131-.
[6]	兰道云, 屈小峰, 唐宇婷, 刘丽英, 刘军. 3.9 V电化学稳定窗口的乙酸盐电解液用于低成本高性能的水系钠离子电池[J]. 电化学（中英文）, 2022, 28(1): 2102231-.
[7]	李姝谨, 曹志康, 王文凯, 张晓菡, 向兴德. 硫酸盐功能电解液增强水系钠离子电池NaTi₂(PO₄)₃/C负极材料电化学性能的研究[J]. 电化学（中英文）, 2021, 27(6): 605-613.
[8]	滕久康, 王庆杰, 张亮, 张红梅, 陈晓涛, 张鹏, 赵金保. 热处理时间对锂电池正极材料Cr₈O₂₁的影响[J]. 电化学（中英文）, 2021, 27(6): 689-697.
[9]	吴凯. Na₃V₂(PO₄)₂O₂F的合成及其在钠离子电池中的应用[J]. 电化学（中英文）, 2021, 27(1): 56-62.
[10]	王存, 张维江, 何腾飞, 雷博, 史尤杰, 郑耀东, 罗伟林, 蒋方明. NCA三元锂离子电池分荷电状态循环的热特性和容量衰退研究[J]. 电化学（中英文）, 2020, 26(6): 777-788.
[11]	段明涛, 蒙延双, 张红帅. Ni₃S₂@碳纳米管复合材料的制备及其储钠性能[J]. 电化学（中英文）, 2020, 26(6): 850-858.
[12]	陈嘉卉, 钟晓斌, 何超, 王晓晓, 许清池, 李剑锋. 中空核壳结构Ni_1.2Co_0.8P@N-C钠离子电池负极材料的制备及拉曼研究[J]. 电化学（中英文）, 2020, 26(3): 328-337.
[13]	王杜丹, 王非, 翟欢欢, 李玉鹏, 杨纳川, 陈康华. 富锂层状正极材料Li₂MnO₃的表面改性及其电化学性能研究[J]. 电化学（中英文）, 2020, 26(2): 289-297.
[14]	王非, 翟欢欢, 王杜丹, 李玉鹏, 陈康华. Sn-Cl共掺杂的锂离子正极材料Li₂MnO₃的结构及电化学性能研究[J]. 电化学（中英文）, 2020, 26(1): 148-155.
[15]	黄云辉. 钴酸锂正极材料与锂离子电池的发展 ——2019年诺贝尔化学奖解读[J]. 电化学（中英文）, 2019, 25(5): 609-613.