硅酸盐学报

同步辐射在锂离子电池材料研究中的应用

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易栖如 ¹ , 李荣荣 ¹ , 孙松 ² , 高琛 ¹

硅酸盐学报 | 综合评述 2026,54(7): 2545-2559

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硅酸盐学报 |综合评述 2026 , 54 (7) : 2545 -2559

同步辐射在锂离子电池材料研究中的应用

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易栖如¹, 李荣荣¹, 孙松², 高琛¹

作者信息

^1．中国科学院大学物理科学学院，北京 101408

^2．安徽大学化学化工学院，合肥 230601

通讯作者:

高琛（1962—），男，博士，教授。

作者简介:

易栖如（1988—），女，助理研究员；

李荣荣（1990—），女，博士。

Application of Synchrotron Radiation in Studies of Li-ion Batteries

Qiru YI¹, Rongrong LI¹, Song SUN², Chen GAO¹

Affiliations

^1.School of Physical Sciences, University of Chinese Academy of Science, Beijing 101408, China

^2.School of Chemistry and Chemical Engineering, Anhui University, Hefei 230601, China

Corresponding Author:

{GAO} Chen (1962-), male, Ph.D., Professor. E-mail: gaochen@ucas.edu.cn

YI Qiru (1988-), female, Assistant Research Fellow. E-mail: yiqiru@ucas.ac.cn;

LI Rongrong (1990-), female, Ph.D. lirongrong@ucas.ac.cn

出版时间: 2026-06-03 doi: 10.14062/j.issn.0454-5648.20250858

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摘要

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二次锂离子电池在交通、电子、电网储能等领域有着广泛的应用。然而，这些规模化的应用依然面临着能量密度、安全性及成本等方面的严峻挑战。突破这些限制或者开发更高性能的材料体系则需要对限制电池性能的材料结构有更加深入的理解。深入理解的关键是发展对材料结构/微结构的高分辨、高灵敏表征方法。同步辐射凭借其单色亮度高、光谱宽等独特优势，在二次锂离子电池的研究中发挥了不可或缺的重要作用。本文总结了近年来同步辐射在锂离子电池材料研究中的应用，探讨了其在揭示电极材料结构演化、界面反应机制及电解质行为等方面的前景，并详细介绍了同步辐射X射线衍射、扩展X射线吸收精细结构、X射线计算机断层扫描以及红外ATR光谱等先进表征方法在典型电池材料研究中的应用实例，展示了这些同步辐射表征技术在解析电池材料充放电过程中的相变、局域结构变化、元素价态分布、界面演化及电解质调控等方面的强大能力。我们相信，同步辐射凭借其高亮度、高分辨率、元素敏感性以及原位/工况的能力，将成为推动高性能电池材料设计与优化的重要工具，在电池材料的多尺度、动态过程研究中发挥重大作用。

关键词

同步辐射 / 二次锂离子电池 / 电极材料 / 原位表征 / 结构演化

Abstract

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Li-ion battery is used in fields such as transportation, electronics, and grid-scale energy storage. However, some challenges remain in achieving higher energy density, enhanced safety, and lower cost for large-scale energy storage and electric vehicles applications. To address these issues, a comprehensive understanding on the structural evolution of electrode materials, the stability of the electrolyte, and the reaction mechanism at the electrode interface is required. Nevertheless, conventional characterizations are limited by brightness, spectral range, and spatial/temporal coherence of light source, thus being unable to resolve the reaction details and structure/micro-structure evolution during the charge/discharge. Synchrotron radiation is an electromagnetic radiation emitted tangentially by relativistic electrons deflecting in a magnetic field. Compared with conventional light sources, synchrotron radiation shows high brightness, highly collimated, wide spectral range, etc.. These superior characters make it a powerful tool for battery study. For instance, synchrotron radiation XRD offers a superior lattice resolution as small as 0.10% or even 0.01%, thereby showing a subtle lattice collapse after lithium de-intercalation. Moreover, synchrotron radiation extended X-ray absorption fine structure (EXAFS) can determine the chemical valence of a selected element and the coordination structure of the element. Furthermore, the EXAFS can be combined with microscopy/imaging to directly provide the spatial distribution of oxidation state and coordination environments of a selected element within electrode materials. This review represents some challenges of Li-ion battery that can be strategically addressed by synchrotron radiation characterizations. In addition, the related progress in this field through a few case studies are described.

Synchrotron Radiation X-ray Diffraction: Compared with conventional X-ray diffraction, synchrotron radiation XRD can accurately capture the subtle lattice changes, phase transformation, and structure/micro-structure evolution during the charge/discharge. For instance, in polycrystalline and single-crystalline NCM523 materials, synchrotron radiation XRD reveals the~0.2% sudden changes in lattice constants and clarifies the significant differences in the phase transformation paths between different crystalline states. Synchrotron radiation XRD can also track the reversible structure evolution from trigonal to cubic to tetragonal during the charge/discharge of the sodium-ion battery cathode material Na_2-_xFe[Fe(CN)₆ · nH₂O, and confirm its excellent structural reversibility and cycling stability.

Synchrotron Radiation Extended X-ray Absorption Fine Structure: The EXAFS can provide the coordination information around a specific element, which is crucial for in-depth research on the structure changes of electrode materials. For instance, regarding the Jahn-Teller distortion of Ni in high-nickel layered cathode materials LiNi_0.9Mn_0.05Co_0.05O₂, the dynamic evolutions of Ni-O coordination environment during the battery cycling can be in-situ monitored. The results demonstrate that the modified coating layer can effectively buffer the Jahn-Teller distortion of Ni³⁺, thereby significantly reducing the lattice distortion and enhancing the structural stability of the high-nickel layered materials. For the issues of Mn dissolution and electrolyte decomposition in the LiNi_0.5Mn_1.5O₄ cathode, the EXAFS characterization confirms that Fe³⁺ in the additive can dynamically and uniformly dope the LNMO cathode, therefore significantly reducing the lattice damage caused by Mn dissolution and improving the cycling stability of the electrode material.

Synchrotron Radiation X-ray Imaging: Synchrotron radiation X-ray computed tomography (XCT) is a high-resolution, non-destructive, three-dimensional characterization technique. Combined with the wavelength tunability of synchrotron radiation, the XCT can dynamically image the internal structural evolution (such as crack propagation, phase distribution) inside the electrode materials and valence and coordination environment distribution through combination with the EXAFS. For instance, in a Li-rich NMC cathode grain, the XCT reveals the gradient distribution of Mn valence and its evolution during the charging/discharging, providing a key basis for understanding the reaction kinetics.

Synchrotron Radiation Infrared Spectroscopy: Attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), as an interface-sensitive technique, can be effectively used to characterize the composition and structure evolution inside the SEI between the electrode and electrolyte. However, as the main vibrational modes of Li salts are located in the low-energy region while conventional Globar gives only a weak output in the corresponding mid-infrared range, high bright synchrotron radiation infrared source is expected to play an important role in the study of SEI. For instance, there is a significant difference between the mid-infrared spectra of LiF thin film obtained from ATR-FTIR and scanning infrared near-field spectroscopy (which should be a surface sensitive technique), indicating that the distribution and coordination environment inside the film is nonuniform. As the gradient is closely related to the reaction/diffusion dynamics, a comprehensive characterization of the distribution of various components eventually bring us a deeper understanding of the formation and dissolution of the Li inorganics in the SEI film.

Summary and prospects

With the growing demand for high-energy-density, long-cycle-life, and low-cost batteries, the design and development of new electrodes/electrolytes become a focus of the energy storage field. However, the complex and variable material systems and the continuous evolution of the structure of active substances during the charge/discharge make their characterization an extremely challenge. As synchrotron radiation provides a high brightness, highly collimated, wide spectral range light source, high spatial/temporal/spectra resolution characterization methods can be developed and applied to the characterization of crystal structure, micro-structure, morphology, coordination environment, valence state of the electrodes/electrolytes as well as their distribution and evolution in the charge/discharge. In this review, we represent the latest progress on the synchrotron radiation based characterizations of electrodes/electrolytes of Li-ion batteries. This review describes the XRD, EXAFS, XCT and ATR-FTIR combined with various in-situ/ex-situ/operando environments. It is expected that the wide application of synchrotron radiation based characterization can prompt the development of key materials for next generation Li-ion batteries.

Key words

synchrotron radiation / lithium-ion batteries / electrode materials / in situ characterization / structural evolution

引用本文

易栖如, 李荣荣, 孙松, 高琛. 同步辐射在锂离子电池材料研究中的应用. 硅酸盐学报, 2026 , 54 (7) : 2545 -2559 . DOI: 10.14062/j.issn.0454-5648.20250858

Qiru YI, Rongrong LI, Song SUN, Chen GAO. Application of Synchrotron Radiation in Studies of Li-ion Batteries[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (7) : 2545 -2559 . DOI: 10.14062/j.issn.0454-5648.20250858

基金

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国家自然基金(52402335)
中国博士后科学基金(2024M753182)

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2026年第54卷第7期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250858

接收时间：2025-11-20
首发时间：2026-10-22
出版时间：2026-06-03

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收稿日期：2025-11-20
修回日期：2026-01-08

基金

国家自然基金(52402335)

中国博士后科学基金(2024M753182)

作者信息

^1．中国科学院大学物理科学学院，北京 101408

^2．安徽大学化学化工学院，合肥 230601

通讯作者:

高琛（1962—），男，博士，教授。

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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