Unravelling thermal behavior change of long-cycled Li-rich cathode by X-ray spectroscopy

IF 4.6 3区材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY

Materials Science and Engineering: B Pub Date : 2025-06-20 DOI:10.1016/j.mseb.2025.118509

Haochong Zhao , Wenxiong Zhang , Hisao Kiuchi , Mustafa Al Samarai , Daobin Liu , Hao Li , Yoshihisa Harada

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Abstract

Thermal stability of layered cathode materials in lithium-ion batteries, such as Li-rich cathode and lithium cobalt oxide, is a critical factor for their commercialization. In this study, we used differential scanning calorimetry (DSC) to investigate the thermal behavior of Li-rich Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ cathode materials at fully charged state (4.8 V) after different cycles. By combining the DSC with X-ray absorption spectroscopy (XAS) and X-ray photoemission spectroscopy, we clarified the relationship among extended cycling impacts on thermal behavior and changes in the valence state of transition metals, surface and bulk structural transformations. The XAS results show valence reduction and spinel-like phase formation at the surface area after long cycles. These structural and electronic transformations align well with the DSC results which show a change of thermal-degradation temperature and decrease of thermal-degradation rate.

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用x射线光谱揭示长循环富锂阴极的热行为变化

锂离子电池层状正极材料（如富锂阴极和锂钴氧化物）的热稳定性是其商业化的关键因素。本研究采用差示扫描量热法（DSC）研究了富锂的Li1.2Ni0.13Co0.13Mn0.54O2正极材料在充满电状态（4.8 V）下经过不同循环后的热行为。通过DSC与x射线吸收光谱（XAS）和x射线光电发射光谱的结合，我们澄清了延长循环对过渡金属的热行为和价态变化、表面和体结构转变之间的关系。XAS结果表明，经过长周期循环后，在表面形成了价态还原和尖晶石样相。这些结构和电子转换与DSC结果一致，显示热降解温度的变化和热降解速率的降低。

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来源期刊

Materials Science and Engineering: B 工程技术-材料科学：综合

CiteScore

5.60

自引率

2.80%

发文量

481

审稿时长

3.5 months

期刊介绍： The journal provides an international medium for the publication of theoretical and experimental studies and reviews related to the electronic, electrochemical, ionic, magnetic, optical, and biosensing properties of solid state materials in bulk, thin film and particulate forms. Papers dealing with synthesis, processing, characterization, structure, physical properties and computational aspects of nano-crystalline, crystalline, amorphous and glassy forms of ceramics, semiconductors, layered insertion compounds, low-dimensional compounds and systems, fast-ion conductors, polymers and dielectrics are viewed as suitable for publication. Articles focused on nano-structured aspects of these advanced solid-state materials will also be considered suitable.