Blaž Tratnik , Sergio Aina , Elena Tchernychova , Matej Gabrijelčič , Gregor Mali , Maria Pilar Lobera , Maria Bernechea , Mathieu Morcrette , Alen Vizintin , Robert Dominko
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Electrochemical analysis demonstrates the improved performance of the hybrid materials over the pristine HC negative electrode and highlights the robustness and stability of the HC/Bi<sub>2</sub>S<sub>3</sub> hybrids over prolonged cycling even under high current densities. Here, the final capacities observed after 100 cycles reached a value of 252 mA h g<sup>−1</sup>, compared to 216 mA h g<sup>−1</sup> of pristine HC. Cyclic voltammetry measurements demonstrate a complex charge storage behavior that integrates both surface and diffusion-driven processes at different potentials during reduction and oxidation. A series of phase transformations during cycling observed in <em>operando</em> XRD expose irreversible reactions during the initial cycle between Bi<sub>2</sub>S<sub>3</sub> and sodium ions, such as the breakdown of the Bi<sub>2</sub>S<sub>3</sub> nanocrystal structure. This phenomenon is further confirmed by the detection of Na<sub>2</sub>S species using <em>ex situ</em> solid-state NMR. High-resolution STEM imaging reveals morphological changes in Bi<sub>2</sub>S<sub>3</sub> nanocrystals and highlights their resistance to pulverization due to their nanoscale dimensions. 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引用次数: 0
摘要
该研究提出了一种适用于钠离子电池负极的硬碳/纳米晶-Bi2S3 混合材料。通过一系列综合分析,包括电化学测量、操作X射线衍射、原位固态核磁共振和高分辨率STEM成像,阐明了HC/Bi2S3混合构型在负电极功能中的有效性,并重点研究了潜在的电荷存储机制。电化学分析表明,与原始碳氢化合物负极相比,混合材料的性能有所提高,并突出了碳氢化合物/Bi2S3 混合材料在高电流密度条件下长时间循环使用时的稳健性和稳定性。在这里,100 次循环后观察到的最终容量达到 252 mA h g-1,而原始 HC 为 216 mA h g-1。循环伏安法测量结果表明,在还原和氧化过程中的不同电位下,电荷存储行为非常复杂,既有表面过程,也有扩散驱动过程。通过操作 XRD 观察到的循环过程中的一系列相变揭示了 Bi2S3 和钠离子之间在初始循环过程中的不可逆反应,例如 Bi2S3 纳米晶体结构的破坏。利用原位固态核磁共振对 Na2S 物种的检测进一步证实了这一现象。高分辨率 STEM 成像揭示了 Bi2S3 纳米晶体的形态变化,并强调了其纳米尺寸所带来的抗粉碎性。这项工作全面揭示了 HC/Bi2S3 的电化学性能,并揭示了循环过程中发生的特定机制和反应。
Exploring hybrid hard carbon/Bi2S3-based negative electrodes for Na-ion batteries†
The study presents a hybrid hard-carbon/nanocrystalline-Bi2S3 material applicable for negative electrodes in sodium-ion batteries. Through a series of comprehensive analyzes, including electrochemical measurements, operando XRD, ex situ solid-state NMR, and high-resolution STEM imaging, the effectiveness of the HC/Bi2S3 hybrid configuration in the negative electrode function is elucidated with a focus on the underlying charge storage mechanism. Electrochemical analysis demonstrates the improved performance of the hybrid materials over the pristine HC negative electrode and highlights the robustness and stability of the HC/Bi2S3 hybrids over prolonged cycling even under high current densities. Here, the final capacities observed after 100 cycles reached a value of 252 mA h g−1, compared to 216 mA h g−1 of pristine HC. Cyclic voltammetry measurements demonstrate a complex charge storage behavior that integrates both surface and diffusion-driven processes at different potentials during reduction and oxidation. A series of phase transformations during cycling observed in operando XRD expose irreversible reactions during the initial cycle between Bi2S3 and sodium ions, such as the breakdown of the Bi2S3 nanocrystal structure. This phenomenon is further confirmed by the detection of Na2S species using ex situ solid-state NMR. High-resolution STEM imaging reveals morphological changes in Bi2S3 nanocrystals and highlights their resistance to pulverization due to their nanoscale dimensions. This work provides comprehensive insights into the electrochemical performance of the HC/Bi2S3 and sheds light on specific mechanisms and reactions occurring during cycling.
期刊介绍:
Green Chemistry is a journal that provides a unique forum for the publication of innovative research on the development of alternative green and sustainable technologies. The scope of Green Chemistry is based on the definition proposed by Anastas and Warner (Green Chemistry: Theory and Practice, P T Anastas and J C Warner, Oxford University Press, Oxford, 1998), which defines green chemistry as the utilisation of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products. Green Chemistry aims to reduce the environmental impact of the chemical enterprise by developing a technology base that is inherently non-toxic to living things and the environment. The journal welcomes submissions on all aspects of research relating to this endeavor and publishes original and significant cutting-edge research that is likely to be of wide general appeal. For a work to be published, it must present a significant advance in green chemistry, including a comparison with existing methods and a demonstration of advantages over those methods.