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Breaking the energy density limit of LiNiO2: Li2NiO3 or Li2NiO2?

打破LiNiO2的能量密度极限: Li2NiO3还是Li2NiO2?

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Abstract

The development of next-generation layered oxide cathodes for high-energy-density electrical vehicle Li-ion batteries (LIBs) is an urgent topic. The existing method is achieved by continuously increasing the Ni contents of Ni-based layered oxides, but it has been limited to LiNiO2. To break this limit and attain increased energy densities, a promising strategy, which involves the introduction of excess Li ions into transition metal (TM) layers to form Li-excess compounds Li2MO3 (M is a TM cation), has attracted enormous interest recently. However, another strategy, which has been neglected in recent years, involves the insertion of an extra layer of Li ions between the TM and original Li layers to form Li2MO2. In this study, typical reversible Li2NiO3 and 1T-Li2NiO2 were selected as two representative cathodes to break the limit of LiNiO2, thereby availing comprehensive comparison with LiNiO2 regarding their overall properties as cathodes from a theoretical perspective. Interestingly, dissimilar to the Ni3+/Ni4+ monoelectron cationic redox associated with LiNiO2, a polaronic anionic redox reaction occurs in Li2NiO3, while a reversible Ni2+/Ni4+ double-electron redox reaction accompanied by insulator-metal transition occurs in Li2NiO2. Owing to this double-electron cationic activity, Li2NiO2 exhibits absolute advantages over the other two materials (LiNiO2 and Li2NiO3) as cathodes for LIBs in terms of the capacity, energy density, electronic conductivity, and thermal stability, thus rendering it the most promising candidate for next-generation layered oxide cathodes with high energy densities to break the limit of LiNiO2.

摘要

开发新一代层状氧化物阴极, 是发展高能量密度电动汽车锂离子电池迫切关注的问题. 目前有一种方法是不断提高镍基层状氧化物中的镍含量, 但这一方法的极限是LiNiO2. 为了突破这一极限, 获得更高的能量密度, 近年来备受关注的一种方法是在过渡金属层中引入过量的锂离子, 形成Li2MO3 (M是过渡金属阳离子). 然而, 还有一种一直被忽视的方法是在过渡金属层和原始Li层之间插入一层额外的Li离子, 形成Li2MO2. 本研究中, 我们选择了典型的Li2NiO3和1T-Li2NiO2作为代表, 从理论角度综合比较了Li2NiO3、 1T-Li2NiO2和LiNiO2的各项电化学性能. 我们发现, 不同于LiNiO2中发生的Ni3+/Ni4+单电子阳离子氧化还原, 在Li2NiO3中存在着伴有极化子的阴离子氧化还原. 而在Li2NiO2中, 则发生了伴有绝缘体到金属转变的Ni2+/Ni4+双电子氧化还原. 在这三种材料中, 由于Li2NiO2具有双电子氧化还原活性, 其在容量、 能量密度、 电导率和热稳定性等方面都表现优异, 是最有希望突破LiNiO2极限的下一代层状氧化物阴极材料. 虽然Li2NiO2具有脱锂过程中的体积变化较大的缺点, 但我们提出了两种可能的解决方法: 在Li层中掺杂Na和在TM层中掺杂Mo, 都获得了不错的效果. 这一工作为如何突破Li-NiO2的能量密度极限, 开发下一代具有高能量密度的层状氧化物阴极提供了新的思路.

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Acknowledgements

This work was financially supported by the starting fund of Peking University, Shenzhen Graduate School and Fujian Science & Technology Innovation Laboratory for Energy Devices of China (21C-LAB).

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Authors and Affiliations

  1. School of Advanced Materials, Peking University, Shenzhen Graduate School, Shenzhen, 518055, China

    Yining Jia  (贾怡宁), Yaokun Ye  (叶耀坤), Jiahua Liu  (刘佳华), Shisheng Zheng  (郑世胜), Weicheng Lin  (林伟成), Zhu Wang  (王竹), Shunning Li  (李舜宁), Feng Pan  (潘锋) & Jiaxin Zheng  (郑家新)

  2. Fujian science & technology innovation laboratory for energy devices of China (21C-LAB), Ningde, 352100, China

    Jiaxin Zheng  (郑家新)

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  1. Yining Jia  (贾怡宁)
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  2. Yaokun Ye  (叶耀坤)
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  3. Jiahua Liu  (刘佳华)
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  4. Shisheng Zheng  (郑世胜)
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  6. Zhu Wang  (王竹)
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  7. Shunning Li  (李舜宁)
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  8. Feng Pan  (潘锋)
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  9. Jiaxin Zheng  (郑家新)
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Contributions

Author contributions Jia Y, Pan F and Zheng J conceived the idea and designed the project. Jia Y performed all the calculations. Ye Y wrote the programs to process the data. Liu J, Zheng S, Lin W, Wang Z, and Li S analyzed the results and participated in the discussion of mechanism. Jia Y and Zheng J wrote the manuscript and all authors edited the manuscript.

Corresponding authors

Correspondence to Feng Pan  (潘锋) or Jiaxin Zheng  (郑家新).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Supplementary information Details for the calculations and supporting data are available in the online version of the paper.

Yining Jia is a master student at the School of Advanced Materials, Peking University, Shenzhen Graduate School. Her research focuses on computational materials and energy materials.

Feng Pan is Chair-Professor, Founding Dean of the School of Advanced Materials, Peking University, Shenzhen Graduate School. He received his PhD degree from the Department of P&A Chemistry, University of Strathclyde, Glasgow, U.K., receiving the “Patrick D. Ritchie Prize” for the best PhD in 1994. Prof. Pan has been engaged in fundamental research and product development of novel optoelectronic and energy storage materials and devices.

Jiaxin Zheng received his PhD degree in condensed physics from Peking University in 2013. He is currently working at the School of Advanced Materials, Peking University as an Associate Professor. His research interests include computational materials and energy materials.

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Jia, Y., Ye, Y., Liu, J. et al. Breaking the energy density limit of LiNiO2: Li2NiO3 or Li2NiO2?. Sci. China Mater. 65, 913–919 (2022). https://doi.org/10.1007/s40843-021-1827-x

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