研究了o3型钠离子层状氧化物阴极材料在高温合成过程中的相变和晶粒生长行为

IF 9.5 2区 材料科学 Q1 CHEMISTRY, PHYSICAL
Anika Tabassum Promi, Junyi Yao, Dawei Xia, Callum Connor, Afolabi Uthmon Olayiwola, Jianming Bai, Chengjun Sun, Dennis Nordlund, Kejie Zhao and Feng Lin
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引用次数: 0

摘要

了解层状氧化物阴极的形成机理是实现其材料性能和电化学行为可控的必要条件。在这项工作中,我们研究了NaNi1/3Fe1/3Mn1/3O2模型钠离子层状氧化物阴极在合成过程中的相和微观结构演变,采用成像,衍射和光谱技术相结合。我们揭示了高温煅烧反应中涉及的合成机理途径,并详细阐述了该材料的合成-微观结构-性能关系。最终层状氧化相的形成涉及到通过硫化氢氧化氧中间体的逐渐转变。反应过程中,前驱体脱水反应在250 ~ 550℃占主导地位,而钠化反应主要发生在550 ~ 850℃。随着相变的多个阶段,最终晶粒结构的形成是通过(003)和(104)晶面的不断生长而发生的。在反应过程中,Mn作为电荷补偿元素,表现出深度依赖的特性。从TM3d-O2p杂化态的光谱特征可以看出,当钠化反应比脱水反应占优势时,反应中间体的电子结构随着温度的升高而逐渐发生变化。煅烧时间也是控制材料微观结构、表面反应性、相分数分布和电化学性能的关键参数。在这里评估的条件下,最佳焙烧时间确定为850℃下18小时。由于Na和O的损失以及钠在颗粒中的不均匀分布,超过这个时间的煅烧被发现对电化学性能有害。我们的工作揭示了钠离子层状氧化物阴极复杂的晶体学-化学-微观结构演变,并为精确调整与电池性能密切相关的材料特性提供了见解。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Elucidating the phase transformations and grain growth behavior of O3-type sodium-ion layered oxide cathode materials during high temperature synthesis†

Elucidating the phase transformations and grain growth behavior of O3-type sodium-ion layered oxide cathode materials during high temperature synthesis†

Elucidating the phase transformations and grain growth behavior of O3-type sodium-ion layered oxide cathode materials during high temperature synthesis†

Understanding the formation mechanism of layered oxide cathodes via solid-state synthesis is imperative to achieving controllability over their materials properties and electrochemical behaviors. In this work, we investigate the phase and microstructure evolution during the synthesis of NaNi1/3Fe1/3Mn1/3O2, a model sodium-ion layered oxide cathode, using a combination of imaging, diffraction, and spectroscopic techniques. We unravel the synthetic mechanistic pathways involved in the high-temperature calcination reaction, as well as elaborate the synthesis-microstructure-performance relationship of this material. The formation of the final layered oxide phase involves a gradual transformation through a sodiated oxyhydroxide intermediate. During the reaction, the precursor dehydration reaction dominates at 250–550 °C, while the major sodiation reaction occurs at 550–850 °C. Alongside multiple stages of phase transformations, the final grain structure formation occurs through the continuous growth of the (003) and (104) facets. During the reaction, Mn acts as the charge-compensating element and exhibits depth-dependent characteristics. When the sodiation reaction dominates over dehydration, the reaction intermediates undergo gradual electronic structure changes with increasing temperature, as indicated by the spectral features of TM3d-O2p hybrid states. Calcination duration is also a critical parameter governing the microstructure, surface reactivity, phase fraction distribution and electrochemical performance of the material. The optimal calcination duration was determined to be 18 hours at 850 °C under the conditions evaluated here. Calcination beyond this duration was found to be detrimental to electrochemical performance due to Na and O loss and heterogeneous sodium distribution throughout the particles. Our work sheds light on the complex crystallographic-chemical-microstructural evolution of sodium ion layered oxide cathodes and provides insight into precisely tuning material properties which are intimately linked to battery performances.

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来源期刊
Journal of Materials Chemistry A
Journal of Materials Chemistry A CHEMISTRY, PHYSICAL-ENERGY & FUELS
CiteScore
19.50
自引率
5.00%
发文量
1892
审稿时长
1.5 months
期刊介绍: The Journal of Materials Chemistry A, B & C covers a wide range of high-quality studies in the field of materials chemistry, with each section focusing on specific applications of the materials studied. Journal of Materials Chemistry A emphasizes applications in energy and sustainability, including topics such as artificial photosynthesis, batteries, and fuel cells. Journal of Materials Chemistry B focuses on applications in biology and medicine, while Journal of Materials Chemistry C covers applications in optical, magnetic, and electronic devices. Example topic areas within the scope of Journal of Materials Chemistry A include catalysis, green/sustainable materials, sensors, and water treatment, among others.
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