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通过溶胶-凝胶技术合成的掺铒LiMn₂O₄正极材料提高循环稳定性

Enhanced Cycling Stability through Erbium Doping of LiMn₂O₄ Cathode Material Synthesized by Sol-Gel Technique.

作者信息

Zhao Hongyuan, Bai Xiuzhi, Wang Jing, Li Dongdong, Li Bo, Wang Yashuang, Dong Li, Liu Binbin, Komarneni Sridhar

机构信息

School of Mechanical & Electrical Engineering, Henan Institute of Science and Technology, Xinxiang 453003, China.

Research Branch of Advanced Materials & Green Energy, Henan Institute of Science and Technology, Xinxiang 453003, China.

出版信息

Materials (Basel). 2018 Aug 29;11(9):1558. doi: 10.3390/ma11091558.

Abstract

In this work, LiMnErO₄ (x ≤ 0.05) samples were obtained by sol-gel processing with erbium nitrate as the erbium source. XRD measurements showed that the Er-doping had no substantial impact on the crystalline structure of the sample. The optimal LiMnErO₄ sample exhibited an intrinsic spinel structure and a narrow particle size distribution. The introduction of Er ions reduced the content of Mn ions, which seemed to efficiently suppress the Jahn⁻Teller distortion. Moreover, the decreased lattice parameters suggested that a more stable spinel structure was obtained, because the Er ions in a ErO₆ octahedra have stronger bonding energy (615 kJ/mol) than that of the Mn ions in a MnO₆ octahedra (402 kJ/mol). The present results suggest that the excellent cycling life of the optimal LiMnErO₄ sample is because of the inhibition of the Jahn-Teller distortion and the improvement of the structural stability. When cycled at 0.5 C, the optimal LiMnErO₄ sample exhibited a high initial capacity of 130.2 mAh g with an excellent retention of 95.2% after 100 cycles. More significantly, this sample showed 83.1 mAh g at 10 C, while the undoped sample showed a much lower capacity. Additionally, when cycled at 55 °C, a satisfactory retention of 91.4% could be achieved at 0.5 C after 100 cycles with a first reversible capacity of 130.1 mAh g.

摘要

在本工作中,以硝酸铒为铒源,通过溶胶-凝胶法制备了LiMnErO₄(x≤0.05)样品。X射线衍射测量表明,铒掺杂对样品的晶体结构没有实质性影响。最佳的LiMnErO₄样品呈现出本征尖晶石结构且粒径分布较窄。铒离子的引入降低了锰离子的含量,这似乎有效地抑制了 Jahn-Teller 畸变。此外,晶格参数的减小表明获得了更稳定的尖晶石结构,因为处于ErO₆八面体中的铒离子具有比处于MnO₆八面体中的锰离子更强的键能(615 kJ/mol)(402 kJ/mol)。目前的结果表明,最佳LiMnErO₄样品优异的循环寿命归因于对 Jahn-Teller 畸变的抑制和结构稳定性的提高。在0.5 C倍率下循环时,最佳的LiMnErO₄样品表现出130.2 mAh g的高初始容量,100次循环后保持率高达95.2%。更显著的是,该样品在10 C倍率下的容量为83.1 mAh g,而未掺杂样品的容量则低得多。此外,在55 °C下循环时,0.5 C倍率下100次循环后可实现91.4%的令人满意的保持率,首次可逆容量为130.1 mAh g。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a03c/6163846/183b0409e1c0/materials-11-01558-g001.jpg

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