NMR Evidence for the Multielectron Reaction Mechanism of Na3V2(PO4)(3) Cathode and the Impact of Polyanion Site Substitution

doi:10.1021/acs.jpcc.1c04099

HFCAS OpenIR

	NMR Evidence for the Multielectron Reaction Mechanism of Na3V2(PO4)(3) Cathode and the Impact of Polyanion Site Substitution
	Qiu, Qing 1; Li, Chao 1; Liu, Hui 1; Liao, Yuxin 1; Zhao, Chong 1; Geng, Fushan 1; Shen, Ming 1; Li, Jingxin 2; Tong, Wei2 ; Hu, Bingwen 1
	2021-07-22
发表期刊	JOURNAL OF PHYSICAL CHEMISTRY C
ISSN	1932-7447
通讯作者	Li, Chao(lchao@phy.ecnu.edu.cn) ; Hu, Bingwen(bwhu@phy.ecnu.edu.cn)
摘要	Although being regarded as a promising cathode candidate for Na-ion batteries, Na3V2(PO4)(3) is still plagued with a congenital drawback that only a limited theoretical specific capacity of 400 Wh kg(-1) can be achieved by employing two-electron reaction. This study focuses on enhancing the energy density by enabling a fourth Na+ intercalation upon discharge, which increases the theoretical specific capacity to around 494 Wh kg(-1). The reaction mechanism of Na3V2(PO4)(3) in the whole potential range of charge/discharge (1.0-3.8 V) is elaborately investigated by the combination of Na-23/P-31 solid-state nuclear magnetic resonance (NMR) and cryogenic-temperature electron paramagnetic resonance (EPR) for the first time. EPR measurement under 1.8 K manifests the generation of V2+ with rhombohedral distortion upon the fourth Na+ intercalation process of Na3V2(PO4)(3). Besides, this study pinpoints the profound impact of polyanion site substitution to the local structural transformation of Na3V2(PO4)(3) upon Na+ (de)intercalation, which corroborates that the boron substitution into phosphorus site can broaden the range of solid-solution reaction, accelerate the structural transition toward V2+-containing phase, and refrain the short scale heterogeneity of P and Na nuclei.
DOI	10.1021/acs.jpcc.1c04099
关键词[WOS]	ELECTROCHEMICAL PERFORMANCE ; ION BATTERIES ; MOBILITY ; NA ; 1ST-PRINCIPLES ; COMPOSITE
收录类别	SCI
语种	英语
资助项目	National Natural Science Foundation of China[21902049] ; National Natural Science Foundation of China[21872055] ; Shanghai Sailing Program[19YF1413000] ; Shanghai Key Laboratory of Magnetic Resonance ; Shanghai Synchrotron Radiation Facility[BL02B02]
项目资助者	National Natural Science Foundation of China ; Shanghai Sailing Program ; Shanghai Key Laboratory of Magnetic Resonance ; Shanghai Synchrotron Radiation Facility
WOS研究方向	Chemistry ; Science & Technology - Other Topics ; Materials Science
WOS类目	Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary
WOS记录号	WOS:000677581600010
出版者	AMER CHEMICAL SOC
引用统计	被引频次：12[WOS] [WOS记录] [WOS相关记录]
文献类型	期刊论文
条目标识符	http://ir.hfcas.ac.cn:8080/handle/334002/124276
专题	中国科学院合肥物质科学研究院
通讯作者	Li, Chao; Hu, Bingwen
作者单位	1.East China Normal Univ, Sch Phys & Elect Sci, Shanghai Key Lab Magnet Resonance, State Key Lab Precis Spect, Shanghai 200241, Peoples R China 2.Chinese Acad Sci, Anhui Key Lab Condensed Matter Phys Extreme Condi, High Magnet Field Lab, Hefei 230031, Peoples R China
推荐引用方式 GB/T 7714	Qiu, Qing,Li, Chao,Liu, Hui,et al. NMR Evidence for the Multielectron Reaction Mechanism of Na3V2(PO4)(3) Cathode and the Impact of Polyanion Site Substitution[J]. JOURNAL OF PHYSICAL CHEMISTRY C,2021,125.
APA	Qiu, Qing.,Li, Chao.,Liu, Hui.,Liao, Yuxin.,Zhao, Chong.,...&Hu, Bingwen.(2021).NMR Evidence for the Multielectron Reaction Mechanism of Na3V2(PO4)(3) Cathode and the Impact of Polyanion Site Substitution.JOURNAL OF PHYSICAL CHEMISTRY C,125.
MLA	Qiu, Qing,et al."NMR Evidence for the Multielectron Reaction Mechanism of Na3V2(PO4)(3) Cathode and the Impact of Polyanion Site Substitution".JOURNAL OF PHYSICAL CHEMISTRY C 125(2021).