Jiabao Li, Jingjing Hao, Quan Yuan, Ruoxing Wang, Frederick Marlton, Tianyi Wang, Chengyin Wang, Xin Guo, Guoxiu Wang
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This work shows discrepancies in the reductive stability of the anionic group, redox kinetics, and component/structure of solid electrolyte interface (SEI) with different salts (NaBF<sub>4,</sub> NaPF<sub>6</sub>, and NaSO<sub>3</sub>CF<sub>3</sub>) in the typical ether solvent (diglyme). Particularly, the density functional theory calculation manifests the preferred decomposition of PF<sub>6</sub><sup>−</sup> due to the reduced reductive stability of anions in the solvation structure, thus leading to the formation of NaF-rich SEI. Further investigation on redox kinetics reveals that the NaPF<sub>6</sub>/diglyme can induce the fast ionic diffusion dynamic and low charge transfer barrier for HC electrode, thus resulting in superior sodium storage performance in terms of rate capability and cycling life, which outperforms those of NaBF<sub>4</sub>/diglyme and NaSO<sub>3</sub>CF<sub>3</sub>/diglyme. 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引用次数: 0
摘要
与广泛使用的酯基电解质相比,硬碳(HC)电极与钠离子电池中的醚基电解质更兼容,可提高循环稳定性和稳健的速率能力。然而,盐阴离子对 HC 电极电化学性能的影响尚待充分了解。本研究系统地探讨了阴离子化学在调节电解质稳定性和钠离子电池性能方面的作用。研究结果表明,在典型的醚溶剂(二甘醇)中,不同盐类(NaBF4、NaPF6 和 NaSO3CF3)的阴离子基团还原稳定性、氧化还原动力学以及固体电解质界面(SEI)的成分/结构存在差异。特别是密度泛函理论计算表明,由于阴离子在溶解结构中的还原稳定性降低,PF6- 会优先分解,从而形成富含 NaF 的 SEI。对氧化还原动力学的进一步研究表明,NaPF6/二甘醇能诱导 HC 电极产生快速的离子扩散动态和较低的电荷转移障碍,因此在速率能力和循环寿命方面具有优于 NaBF4/diglyme 和 NaSO3CF3/diglyme 的储钠性能。重要的是,这项研究为通过调节电解质中的阴离子基团来优化电极材料的电化学行为提供了宝贵的见解。
The effect of salt anion in ether-based electrolyte for electrochemical performance of sodium-ion batteries: A case study of hard carbon
Compared with the extensively used ester-based electrolyte, the hard carbon (HC) electrode is more compatible with the ether-based counterpart in sodium-ion batteries, which can lead to improved cycling stability and robust rate capability. However, the impact of salt anion on the electrochemical performance of HC electrodes has yet to be fully understood. In this study, the anionic chemistry in regulating the stability of electrolytes and the performance of sodium-ion batteries have been systematically investigated. This work shows discrepancies in the reductive stability of the anionic group, redox kinetics, and component/structure of solid electrolyte interface (SEI) with different salts (NaBF4, NaPF6, and NaSO3CF3) in the typical ether solvent (diglyme). Particularly, the density functional theory calculation manifests the preferred decomposition of PF6− due to the reduced reductive stability of anions in the solvation structure, thus leading to the formation of NaF-rich SEI. Further investigation on redox kinetics reveals that the NaPF6/diglyme can induce the fast ionic diffusion dynamic and low charge transfer barrier for HC electrode, thus resulting in superior sodium storage performance in terms of rate capability and cycling life, which outperforms those of NaBF4/diglyme and NaSO3CF3/diglyme. Importantly, this work offers valuable insights for optimizing the electrochemical behaviors of electrode materials by regulating the anionic group in the electrolyte.
期刊介绍:
Carbon Energy is an international journal that focuses on cutting-edge energy technology involving carbon utilization and carbon emission control. It provides a platform for researchers to communicate their findings and critical opinions and aims to bring together the communities of advanced material and energy. The journal covers a broad range of energy technologies, including energy storage, photocatalysis, electrocatalysis, photoelectrocatalysis, and thermocatalysis. It covers all forms of energy, from conventional electric and thermal energy to those that catalyze chemical and biological transformations. Additionally, Carbon Energy promotes new technologies for controlling carbon emissions and the green production of carbon materials. The journal welcomes innovative interdisciplinary research with wide impact. It is indexed in various databases, including Advanced Technologies & Aerospace Collection/Database, Biological Science Collection/Database, CAS, DOAJ, Environmental Science Collection/Database, Web of Science and Technology Collection.