Nuclear magnetic resonance spectroscopy for probing interfaces in electrochemical energy storage systems

doi:10.19799/j.cnki.2095-4239.2023.0816

Abstract

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

CLC Number:

TQ 152

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.

Figures/Tables 7

Table 1

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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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