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

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.

doi:10.1038/s41467-019-09248-0

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

Journal Article · Tue Apr 09 00:00:00 EDT 2019 · Nature Communications

DOI:https://doi.org/10.1038/s41467-019-09248-0· OSTI ID:1542396

Lin, Ruoqian ^[1];

^[2]; Liu, Mingjie ^[1]; Wang, Yi ^[3]; Cheng, Hao ^[4]; Wu, Jinpeng ^[5];

^[6];

^[1]; Bak, Seongmin ^[2]; Tong, Xiao ^[1]; Zhang, Rui ^[7];

^[5];

^[8];

^[3]; Yang, Xiao-Qing ^[2];

^[9]

Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division
Chinese Academy of Sciences (CAS), Beijing (China). Beijing Advanced Innovation Center for Materials Genome Engineering, Inst. of Physics
Xiamen Univ., Xiamen (China). Dept. of Physics and the Collaborative Innovation Center for Optoelectronic Semiconductors and Efficient Devices
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Xiamen Univ., Xiamen (China). Dept. of Physics and the Collaborative Innovation Center for Optoelectronic Semiconductors and Efficient Devices; Xiamen Univ. Malaysia, Selangor (Malaysia)
Univ. of California, Irvine, CA (United States). Dept. of Physics and Astronomy
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
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

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, Li₂Ru_0.5Mn_0.5O₃. 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.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)

Grant/Contract Number:: AC02-05CH11231; SC0012704

OSTI ID:: 1542396

Alternate ID(s):: OSTI ID: 1507699

Report Number(s):: BNL-211556-2019-JAAM; ark:/13030/qt9p5140p2

Journal Information:: Nature Communications, Vol. 10, Issue 1; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 53 works

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