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Anomalous metal segregation in lithium-rich material provides design rules for stable cathode in lithium-ion battery

Lin R 1 , Hu E 2 , Liu M 1 , Wang Y 3 , Cheng H 4 , Wu J 5 Show all authors , Zheng JC 4 , Wu Q 1 , Bak S 2 , Tong X 1 , Zhang R 6 , Yang W 5 , Persson KA 7 , Yu X 8 , Yang XQ 9 , Xin HL 10

Affiliations 

  • 1 Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY, 11973, USA
  • 2 Chemistry Division, Brookhaven National Laboratory, Upton, NY, 11973, USA
  • 3 Beijing Advanced Innovation Center for Materials Genome Engineering, Institute of Physics, Chinese Academy of Sciences, 100190, Beijing, China
  • 4 Department of Physics and the Collaborative Innovation Center for Optoelectronic Semiconductors and Efficient Devices, Xiamen University, 361005, Xiamen, China
  • 5 Advanced Light Source, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, CA, 94720, USA
  • 6 Department of Physics and Astronomy, University of California, Irvine, CA, 92697, USA
  • 7 Energy Storage and Distributed Resources Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA
  • 8 Beijing Advanced Innovation Center for Materials Genome Engineering, Institute of Physics, Chinese Academy of Sciences, 100190, Beijing, China. [email protected]
  • 9 Chemistry Division, Brookhaven National Laboratory, Upton, NY, 11973, USA. [email protected]
  • 10 Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY, 11973, USA. [email protected]
Nat Commun, 2019 04 09;10(1):1650.
PMID: 30967531 DOI: 10.1038/s41467-019-09248-0

Abstract

Despite the importance of studying the instability of delithiated cathode materials, it remains difficult to underpin the degradation mechanism of lithium-rich cathode materials due to the complication of combined chemical and structural evolutions. Herein, we use state-of-the-art electron microscopy tools, in conjunction with synchrotron X-ray techniques and first-principle calculations to study a 4d-element-containing compound, Li2Ru0.5Mn0.5O3. We find surprisingly, after cycling, ruthenium segregates out as metallic nanoclusters on the reconstructed surface. Our calculations show that the unexpected ruthenium metal segregation is due to its thermodynamic insolubility in the oxygen deprived surface. This insolubility can disrupt the reconstructed surface, which explains the formation of a porous structure in this material. This work reveals the importance of studying the thermodynamic stability of the reconstructed film on the cathode materials and offers a theoretical guidance for choosing manganese substituting elements in lithium-rich as well as stoichiometric layer-layer compounds for stabilizing the cathode surface.

* Title and MeSH Headings from MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine.

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