电化学(中英文) ›› 2022, Vol. 28 ›› Issue (2): 2108421. doi: 10.13208/j.electrochem.210842
所属专题: “下一代二次电池”专题文章
收稿日期:
2021-08-21
修回日期:
2021-09-08
出版日期:
2022-02-28
发布日期:
2021-09-17
通讯作者:
胡炳文
E-mail:bwhu@phy.ecnu.edu.cn
Bing-Wen Hu*(), Chao Li, Fu-Shan Geng, Ming Shen
Received:
2021-08-21
Revised:
2021-09-08
Published:
2022-02-28
Online:
2021-09-17
Contact:
Bing-Wen Hu
E-mail:bwhu@phy.ecnu.edu.cn
摘要:
金属离子电池改变了我们的日常生活。金属离子电池里的电极材料研究是提高电池性能的关键。因此,深刻理解电极材料的结构-性能关系,有助于提高材料的能量密度和功率密度。磁共振,包括核磁共振(NMR)和电子顺磁共振(EPR),在过去的三十年中不断得到改进,并逐渐成为研究电极材料结构性能关系的重要技术之一。本文总结了我们课题组在几种有趣的电极材料上的磁共振研究进展,阐释了NMR和EPR在电极材料研究中的重要作用。本文将有助于把握磁共振技术对电池研究的重要价值,促进磁共振技术的进一步发展。
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.
Bing-Wen Hu, Chao Li, Fu-Shan Geng, Ming Shen. Magnetic Resonance in Metal-Ion Batteries: From NMR (Nuclear Magnetic Resonance) to EPR (Electron Paramagnetic Resonance)[J]. Journal of Electrochemistry, 2022, 28(2): 2108421.
Figure 2.
In-situ EPR spectra of the NaCrO2/Na cell cycled at 10 mA·g-1 between (A) 2.2 ~ 3.6 V and (C) 2.2 ~ 4.5 V. The intensive Na signal in the range of 331 ~ 335 mT is truncated for clarity. (B, D) Corresponding voltage profiles (top) and EPR intensities (bottom) as a function of time. EPR intensities are calculated using half of the peak-to-peak intensity. (Reproduced from Ref.[21] with permission from American Chemical Society) (color on line)
Figure 3.
In-situ EPR images of the in-situ cell charged to 4.15 V on (A) the ZY plane and (B) the XY plane. Color bars on the right side show the normalized intensity of spin concentrations. (C) Digital photos of the cell used in EPR imaging. The sizes of the cathode and the separator are marked in blue and red, respectively. (D) Scheme for the orientation of the cell in the image coordinates. (Reproduced from Ref.[21] with permission from American Chemical Society) (color on line)
Figure 5.
(A) X-band EPR spectra for lithiation/delithiation of the r-CoHNta electrode materials cycled to different states-of-charge recorded at 2 K; (B) The corresponding electrochemical profile cycled at a current rate of 100 mA·g-1. (Reproduced from Ref.[24] with permission from Elsevier publisher) (color on line)
Figure 6.
(A) 23Na and (B) 31P MAS ssNMR spectra of NVOPF, NV3.8OPF, and NV3.6OPF. Spinning sidebands are marked with asterisks in (A) and (B). (C) Continuous-wave X-band EPR spectra recorded at 2 K of NVOPF, NV3.8OPF, and NV3.6OPF. (D) An enlarged EPR spectrum of NV3.8OPF. (Reproduced with permission from ref.[28], Copyright 2018, The Royal Society of Chemistry) (color on line)
Figure 7.
(A) 23Na MAS ssNMR spectra of the NV3.8POF electrodes under various SOC (states-of-charge) values during charge process; (B) Parallel-mode EPR spectra of cycled NV3.8POF under representative SOC. (Reprinted with permission from ref.[29], Copyright 2018, American Chemical Society) (color on line)
Figure 8.
Isotropic slices of 7Li pj-MATPASS NMR spectra for (A, C) pristine NLMO, and NLMTO-0.1, and (B, D) fully discharged NLMO and NLMTO-0.1 electrodes. The resonances within the blue-marked region correspond to the Li sites in the Na layer, while the resonances within the yellow-marked region correspond to the Li sites within the TMO2 layer. (Reproduced from Ref.[32] with permission from American Chemical Society) (color on line)
Figure 9.
(A) Fine scanning vertical-mode EPR spectra of cycled NLMO under the representative SoC; The O2n- EPR signals possess various hyperfine patterns. (B) Fine scanning vertical-mode EPR spectra of cycled NLMTO-0.1. (Reproduced from Ref.[32] with permission from American Chemical Society) (color on line)
Figure 10.
Ex-situ perpendicular-mode CW-EPR spectra of LTMO during the processes of (A) Mn oxidation, (B) O oxidation, and (C) reduction. These EPR measurements were performed at 1.8 K. Signal intensities are normalized based on the mass of each material scraped from the electrodes. The sharp signals centered at ~ 345 mT (g ~ 2.0) stem from the delocalized electrons in the conductive carbon black, which can be regarded as an external reference although it may cover up similar signals. (Reproduced from Ref.[34] with permission from The Royal Society of Chemistry) (color on line)
Table 1
Summary of important magnetic resonance techniques and their applications
Technique | Application |
---|---|
MQMAS (multiple-quantum magic angle spinning) | Obtain high-resolution 2D NMR spectra of half-integer quadrupolar nuclei, e.g., 23Na(Na3V2(PO4)2F3-2yO2y), 17O. |
pjMATPASS (projected magic-angle-turning phase-adjusted- sideband-separation) | Obtain high-resolution NMR spectra with large chemical- shift-anisotropy broadening due to hyperfine interactions, e.g., 7Li(Na0.72Li0.24Mn0.76O2), 31P, 19F(Na3V2(PO4)2F3-2yO2y). |
WURST-CPMG(wideband uniform rate smooth truncation Carr-Purcell Meiboom-Gil) | Obtain static broad NMR spectra, e.g., 14N, 95Mo (MoS2). |
2D homonuclear correlation and exchange (2D EXSY) | Study dynamic or chemical exchange processes, e.g., 7Li and 23Na. |
2D homonuclear correlation based on dipole coupling (i.e. RFDR) | Detect neighboring atoms in space to reveal the spatial proximity, e.g., 1H, 7Li, and 31P. |
Perpendicular mode EPR | Detect the transitions between eigenstates for systems with half-integer spin, e.g., V4+. |
Parallel mode EPR | Detect the transitions between eigenstates for systems with integer spin, e.g., V3+. |
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