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

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, Li 2Ru 0.5Mn 0.5O 3. 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.

Authors:
 [1]; ORCiD logo [2];  [1];  [3];  [4];  [5]; ORCiD logo [6]; ORCiD logo [1];  [2];  [1];  [7]; ORCiD logo [5]; ORCiD logo [8]; ORCiD logo [3];  [2]; ORCiD logo [9]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division
  3. Chinese Academy of Sciences (CAS), Beijing (China). Beijing Advanced Innovation Center for Materials Genome Engineering, Inst. of Physics
  4. Xiamen Univ., Xiamen (China). Dept. of Physics and the Collaborative Innovation Center for Optoelectronic Semiconductors and Efficient Devices
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  6. Xiamen Univ., Xiamen (China). Dept. of Physics and the Collaborative Innovation Center for Optoelectronic Semiconductors and Efficient Devices; Xiamen Univ. Malaysia, Selangor (Malaysia)
  7. Univ. of California, Irvine, CA (United States). Dept. of Physics and Astronomy
  8. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Storage and Distributed Resources Division; Univ. of California, Berkeley, CA (United States). Dept. of Materials Science
  9. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Univ. of California, Irvine, CA (United States). Dept. of Physics and Astronomy
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1507699
Report Number(s):
BNL-211556-2019-JAAM
Journal ID: ISSN 2041-1723
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE

Citation Formats

Lin, Ruoqian, Hu, Enyuan, Liu, Mingjie, Wang, Yi, Cheng, Hao, Wu, Jinpeng, Zheng, Jin-Cheng, Wu, Qin, Bak, Seongmin, Tong, Xiao, Zhang, Rui, Yang, Wanli, Persson, Kristin A., Yu, Xiqian, Yang, Xiao-Qing, and Xin, Huolin L.. Anomalous metal segregation in lithium-rich material provides design rules for stable cathode in lithium-ion battery. United States: N. p., 2019. Web. doi:10.1038/s41467-019-09248-0.
Lin, Ruoqian, Hu, Enyuan, Liu, Mingjie, Wang, Yi, Cheng, Hao, Wu, Jinpeng, Zheng, Jin-Cheng, Wu, Qin, Bak, Seongmin, Tong, Xiao, Zhang, Rui, Yang, Wanli, Persson, Kristin A., Yu, Xiqian, Yang, Xiao-Qing, & Xin, Huolin L.. Anomalous metal segregation in lithium-rich material provides design rules for stable cathode in lithium-ion battery. United States. doi:10.1038/s41467-019-09248-0.
Lin, Ruoqian, Hu, Enyuan, Liu, Mingjie, Wang, Yi, Cheng, Hao, Wu, Jinpeng, Zheng, Jin-Cheng, Wu, Qin, Bak, Seongmin, Tong, Xiao, Zhang, Rui, Yang, Wanli, Persson, Kristin A., Yu, Xiqian, Yang, Xiao-Qing, and Xin, Huolin L.. Tue . "Anomalous metal segregation in lithium-rich material provides design rules for stable cathode in lithium-ion battery". United States. doi:10.1038/s41467-019-09248-0. https://www.osti.gov/servlets/purl/1507699.
@article{osti_1507699,
title = {Anomalous metal segregation in lithium-rich material provides design rules for stable cathode in lithium-ion battery},
author = {Lin, Ruoqian and Hu, Enyuan and Liu, Mingjie and Wang, Yi and Cheng, Hao and Wu, Jinpeng and Zheng, Jin-Cheng and Wu, Qin and Bak, Seongmin and Tong, Xiao and Zhang, Rui and Yang, Wanli and Persson, Kristin A. and Yu, Xiqian and Yang, Xiao-Qing and Xin, Huolin L.},
abstractNote = {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.},
doi = {10.1038/s41467-019-09248-0},
journal = {Nature Communications},
number = 1,
volume = 10,
place = {United States},
year = {2019},
month = {4}
}

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Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009

  • Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
  • Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
  • DOI: 10.1088/0953-8984/21/39/395502

Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998

  • Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
  • Physical Review B, Vol. 57, Issue 3, p. 1505-1509
  • DOI: 10.1103/PhysRevB.57.1505

PDFgetX2: a GUI-driven program to obtain the pair distribution function from X-ray powder diffraction data
journal, July 2004

  • Qiu, Xiangyun; Thompson, Jeroen W.; Billinge, Simon J. L.
  • Journal of Applied Crystallography, Vol. 37, Issue 4, p. 678-678
  • DOI: 10.1107/S0021889804011744

High Capacity, Surface-Modified Layered Li [Li (1?x) ? 3Mn (2?x) ? 3Nix ? 3Cox ? 3 ] O2 Cathodes with Low Irreversible Capacity Loss
journal, March 2006

  • Wu, Y.; Manthiram, A.
  • Electrochemical and Solid-State Letters, Vol. 9, Issue 5, p. A221-A224
  • DOI: 10.1149/1.2180528

Electrochemical and Structural Properties of xLi2M�O3 �(1? x )LiMn0.5Ni0.5O2 Electrodes for Lithium Batteries (M� = Ti, Mn, Zr; 0 ? x ? 0.3)
journal, May 2004

  • Kim, Jeom-Soo; Johnson, Christopher S.; Vaughey, John T.
  • Chemistry of Materials, Vol. 16, Issue 10, p. 1996-2006
  • DOI: 10.1021/cm0306461

Two-dimensional detector software: From real detector to idealised image or two-theta scan
journal, January 1996

  • Hammersley, A. P.; Svensson, S. O.; Hanfland, M.
  • High Pressure Research, Vol. 14, Issue 4-6, p. 235-248
  • DOI: 10.1080/08957959608201408