波谱学杂志

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低场固体核磁共振魔角旋转探头关键部件的研制

吴肇博1#,王佳鑫2#,刘万震2,3,程鑫2,3,魏巍1,黄臻1,陈方2,3,张志2,3*,刘朝阳2,3§   

  1. 1. 武汉轻工大学电气与电子工程学院,湖北 武汉 430023;2. 中国科学院精密测量科学与技术创新研究院,磁共振波谱与成像全国重点实验室,武汉磁共振中心,湖北 武汉 43007;3. 中国科学院大学,北京 100049

  • 收稿日期:2025-04-27 修回日期:2025-05-19 出版日期:2025-06-04 在线发表日期:2025-06-04
  • 通讯作者: 张志;刘朝阳 E-mail:zhangzhi@apm.ac.cn;chyliu@apm.ac.cn

Design and Development of Key Components for a Low-Field Solid-State NMR Magic Angle Spinning (MAS) Probe

WU Zhaobo1#,WANG Jiaxin2#,LIU Wanzhen2,3,CHENG Xin2,3,WEI Wei1,HUANG Zhen1,CHEN Fang2,3,ZHANG Zhi2,3*,LIU Chaoyang2,3§   

  1. 1. School of Electrical and Electronic Engineering, Wuhan Polytechnic University, Wuhan 430023, China; 2. State Key Laboratory of Magnetic Resonance Spectroscopy and Imaging, National Center for Magnetic Resonance in Wuhan, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, Wuhan 430071, China; 3. University of Chinese Academy of Sciences, Beijing 100049, China

  • Received:2025-04-27 Revised:2025-05-19 Published:2025-06-04 Online:2025-06-04
  • Contact: ZHANG Zhi;LIU Chaoyang E-mail:zhangzhi@apm.ac.cn;chyliu@apm.ac.cn

摘要: 高场固体核磁共振技术(SSNMR)因其具有高灵敏度和多核检测能力,是固体材料的微观结构解析和分子动力学行为研究的重要的表征手段。然而,对于一些锂离子电池之类的顺磁材料,材料中普遍存在的过渡金属离子(如Mn3+、Fe3+等)赋予体系强顺磁特性,在高场条件下将面临磁场不均匀、谱线展宽、信号衰减、无法魔角旋转等一系列挑战,从而导致难以获取有用的信息。低场下由于顺磁效应引起的磁场畸变显著减弱,有望解决顺磁样品在高场核磁共振中分辨率降低或无法魔角旋转的问题。本文通过理论分析低场环境对顺磁物质研究的优势,研制了用于0.5T Halbach磁体的低场固体MAS探头,主要包括MAS单元的小型化设计、气动驱动气路的有限元仿真优化、射频线圈参数的仿真分析等研究工作,并与谱仪控制单元、磁体单元、气动控制单元等集成为一套完整的低场固体MAS谱仪,实现了低场条件下的锂离子电池MAS NMR测试。并在12kHz转速下采集到多种顺磁样品7Li的NMR信号,验证了自主研制的低场固体MAS探头在低场下对顺磁样品进行固体高分辨率NMR采集的可行性,解决了高场条件下顺磁样品自旋边带叠加,或无法魔角旋转等问题,为顺磁样品的NMR研究提供了新方案。

关键词: 固体核磁共振, 低场核磁共振, 魔角旋转技术(MAS), 低场MAS, 射频线圈

Abstract: High-field solid-state nuclear magnetic resonance (SSNMR) technology, due to its high sensitivity and multi-nuclear detection capabilities, is an important characterization method for the analysis of the microstructure of solid materials and the study of molecular dynamics behavior. However, for some paramagnetic materials such as lithium-ion batteries, the transition metal ions (such as Mn3+, Fe3+, etc.) commonly present in the materials endow the system with strong paramagnetic properties. Under high-field conditions, it will face a series of challenges such as magnetic field inhomogeneity, spectral line broadening, signal attenuation, and the inability to perform magic angle spinning. As a result, it is difficult to obtain useful information. Under low-field conditions, the magnetic field distortion caused by the paramagnetic effect is significantly weakened, which is expected to solve the problems of reduced resolution or the inability to perform magic angle spinning of paramagnetic samples in high-field nuclear magnetic resonance. This paper analyzes the advantages of a low-field environment for the study of paramagnetic substances through theoretical analysis, and develops a low-field solid-state MAS probe for a 0.5T Halbach magnet. It mainly includes research work such as the miniaturization design of the MAS unit, the finite element simulation optimization of the pneumatic drive gas circuit, and the simulation analysis of the parameters of the radio frequency coil. It is integrated with the spectrometer control unit, magnet unit, gas circuit control unit, etc. to form a complete low-field solid-state MAS spectrometer, realizing the MAS NMR testing of lithium-ion batteries under low-field conditions. Moreover, the NMR signals of 7Li of various paramagnetic samples are collected at a rotation speed of 12kHz, verifying the feasibility of the self-developed low-field solid-state MAS probe for solid high-resolution NMR acquisition of paramagnetic samples under low-field conditions. It solves the problems of the superposition of spinning sidebands of paramagnetic samples or the inability to perform magic angle spinning under high-field conditions, providing a new solution for the NMR study of paramagnetic samples.

Key words: Solid-state NMR, Low-field NMR, Magic angle spinning technology (MAS), Low-field MAS, Radio frequency coil

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