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First-principles computational studies on Na+ diffusion in Li-doped P3-type NaMnO2 as cathode material for Na-ion batteries

锂离子掺杂P3型NaMnO2钠离子电池正极材料中Na+扩散的第一性原理计算研究

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Abstract

Na-ion diffusion kinetics is a key factor that decided the charge/discharge rate of the electrode materials in Na-ion batteries. In this work, two extreme concentrations of NaMnO2 and Na2/3Li1/6Mn5/6O2 are considered, namely, the vacancy migration of Na ions in the fully intercalated and the migration of Na ions in the fully de-intercalated. The Na-vacancy and Na+ distribution in NaMnO2 migrated along oxygen dumbbell hop (ODH) and tetrahedral site hop (TSH), and the migration energy barriers were 0.374 and 0.296 eV, respectively. In NaLi1/6Mn5/6O2, the inhomogeneity of Li doping leads to the narrowing of the interlayer spacing by 0.9% and the increase of the energy barrier by 53.8%. On the other hand, due to the alleviation of Jahn-Teller effect of neighboring Mn, the bonding strength of Mn-O was enhanced, so that the energy barrier of path 2–3 in Mn-L1 and Mn-L2 was the lowest, which was 0.234 and 0.424 eV, respectively. In Na1/6Li1/6Mn5/6O2, the migration energy barriers of Na-L2 and Na-L3 are 1.233 and 0.779 eV, respectively, because Li+ migrates from the transition (TM) layer to the alkali metal (AM) layer with Na+ migration, which requires additional energy.

摘要

钠离子扩散动力学是决定钠离子电池电极材料充放电速率的关键因素。本文考虑了NaMnO2 和Na2/3Li1/6Mn5/6O2 的两种极端浓度,即完全嵌入的Na+空位迁移和完全脱嵌的Na+迁移。NaMnO2 中的空位和钠离子分布沿着氧哑铃位迁移和四面体位迁移,迁移能垒分别为0.374 和0.296 eV。在NaLi1/6Mn5/6O2中,一方面由于Li 掺杂的不均匀性导致被掺杂层的层间距变窄0.9%,能垒增加53.8%;另一方面由于缓解邻近Mn 的Jahn-Teller 效应强化了Mn-O 成键强度,使得Mn-L1 和Mn-L2 中path2-3 能垒最低,分别为0.234 和0.424 eV。在Na1/6Li1/6Mn5/6O2中,Na-L2 和Na-L3 迁移能垒分别为1.233 和0.779 eV,这是因为随着Na+迁移,Li+会从过渡金属层向碱金属层迁移,从而需要额外的能量。

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Authors and Affiliations

  1. School of Metallurgy and Environment, Central South University, Changsha, 410083, China

    Yu Zhang  (张禹), Jie Li  (李劼), Hong-liang Zhang  (张红亮), Ke Du  (杜柯), Xiang-yuan Zhou  (周湘远) & Jing-kun Wang  (王景坤)

  2. Hongqiao Group Limited, Huixian First Road, Zouping Economic Development Zone, Zouping, 256200, China

    Jing-kun Wang  (王景坤)

Authors
  1. Yu Zhang  (张禹)
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  2. Jie Li  (李劼)
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  3. Hong-liang Zhang  (张红亮)
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  4. Ke Du  (杜柯)
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  5. Xiang-yuan Zhou  (周湘远)
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  6. Jing-kun Wang  (王景坤)
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Contributions

The overarching research goals were developed by ZHANG Yu, LI Jie, ZHANG Hong-liang and DU Ke. LI Jie, ZHANG Hong-liang and DU Ke provided the computing resources and methods. ZHANG Yu, ZHOU Xiang-yuan and WANG Jing-kun established the models and analyzed the calculated data. The initial draft of the manuscript was written by ZHANG Yu and DU Ke. All authors replied to reviewers’ comments and revised the final version.

Corresponding authors

Correspondence to Hong-liang Zhang  (张红亮) or Ke Du  (杜柯).

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Conflict of interest

ZHANG Yu, LI Jie, ZHANG Hong-liang, DU Ke, ZHOU Xiang-yuan and WANG Jing-kun declare that they have no conflict of interest.

Foundation item: Projects(51602352, 51974373, 51874358, 51772333, 61533020) supported by the National Natural Science Foundation of China; Project(2019JZZY020123) supported by the Major Scientific and Technological Innovation Projects of Shandong Province, China

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Zhang, Y., Li, J., Zhang, Hl. et al. First-principles computational studies on Na+ diffusion in Li-doped P3-type NaMnO2 as cathode material for Na-ion batteries. J. Cent. South Univ. 29, 2930–2939 (2022). https://doi.org/10.1007/s11771-022-5137-z

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