电化学储能界面的核磁共振谱学研究方法

doi:10.19799/j.cnki.2095-4239.2023.0816

摘要/Abstract

摘要：

深入认识电化学储能体系(如锂离子电池与锂金属电池等)表界面层的组成与结构，以及相关的物质传递、电荷存储与转移机理，对于开发宽温区、长循环与高倍率电化学储能器件具有重要的理论指导价值。电化学表界面层呈现出稀薄、无序和敏感等特征，直接观测并获取准确信息充满了挑战。在众多表征技术中，核磁共振技术表现出非侵入性和可定量等特点，是物质鉴别以及微观结构与动力学研究的重要手段。利用原位电化学核磁共振技术还能够观测电化学表界面生成的亚稳态中间相或发生的动态结构演变，为电化学储能体系表界面研究提供了独特而关键的见解。本文综述了电化学储能界面的典型核磁共振研究方法，着重介绍了一维与二维核磁共振技术、同位素示踪技术、动态核极化技术和交叉极化技术以及原位电化学核磁共振技术等方法的基本原理与应用策略。通过上述方法在电极与电解质、复合固态电解质等界面的组成结构、离子输运与界面电荷存储机理等电化学储能界面的应用实例，展示了核磁共振技术在电化学储能界面研究中的应用潜力和重要研究成果。

关键词: 界面电化学, 电化学原位核磁共振, 离子输运, 电化学储能

Abstract:

A comprehensive understanding of the composition, structure, and correlated mass transfer and charge storage mechanisms at the interface of electrochemical energy storage systems (such as lithium-ion batteries and lithium metal batteries) is crucial for enhancing their cycling and rate performances over a wide temperature range. However, the inherent characteristics of these interfaces, such as thinness, disorderedness, and sensitivity, pose significant challenges for direct observation and precise characterization. Among the various available characterization techniques, nuclear magnetic resonance (NMR) spectroscopy stands out because of its unique ability to noninvasively and quantitatively identify interfacial components and achieve microstructural and microscopic dynamics. Moreover, in-situ electrochemical NMR spectroscopy has demonstrated great potential for investigating short-life intermediates and dynamic structural transformations at the interfaces of electrochemical energy-storage systems, offering crucial insights into the physicochemical properties and fundamental theories of these interfaces. This study presents a comprehensive review of NMR research methods for electrochemical energy storage interfaces. This study emphasizes the basic principles and application strategies of one-and two-dimensional NMR, isotope-tracer techniques, dynamic nuclear polarization, cross-polarization, and in-situ electrochemical NMR techniques. Examples are provided to enumerate the application of these methods in analyzing the compositional structures and interface ion transport of electrode-electrolyte and composite solid-state electrolyte interfaces as well as the charge storage mechanisms at the interface. These examples demonstrate the application potential and the research outcomes of NMR techniques for studying interfaces in electrochemical energy storage systems.

Key words: interfacial electrochemistry, in-situ electrochemical nuclear magnetic resonance, electrochemical energy storage, ionic transport

中图分类号:

TQ 152

欧阳意梅, 赵蒙蒙, 钟贵明, 彭章泉. 电化学储能界面的核磁共振谱学研究方法[J]. 储能科学与技术, 2024, 13(1): 157-166.

Yimei OUYANG, Mengmeng ZHAO, Guiming ZHONG, Zhangquan PENG. Nuclear magnetic resonance spectroscopy for probing interfaces in electrochemical energy storage systems[J]. Energy Storage Science and Technology, 2024, 13(1): 157-166.

图/表 7

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核磁同位素	自旋量子数	天然丰度/%	四极矩Q/fm²	灵敏度	应用	识别界面物种	参考文献
¹H	1/2	99.98	—	高	化学位移识别界面有机物、含氢无机物	LiOH、LiH、HCO₂Li、CH₃OLi、CH₃OCO₂Li等	^[19]
⁷Li	3/2	92.41	-4.01	高	化学位移和四极耦合用于识别无机相	LiF、Li₂CO₃、LiOH、LiH、Li₂O等	^[19]
¹³C	1/2	1.07	—	低	化学位移识别界面无机相(辅助同位素富集、交叉极化、动态核极化技术提高灵敏度)	CH₃OLi、HCO₂Li、CH₃R、R'CH₂R、 CH₃OCO₂Li、Li₂CO₃等	^[21]
¹⁹F	1/2	100	—	高	化学位移识别界面含氟无机物、有机物	LiF、RPO₃F、RPO₂F₂等	^[24]
²³Na	3/2	100	10.4	高	化学位移和四极耦合用于识别无机相	NaF、Na₂CO₃、NaOH、NaH、Na₂O等	^[25-26]
³¹P	1/2	100	—	高	化学位移识别界面含磷无机相	RPO₃F、RPO₂F₂等	^[27]

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