Correlation between manganese dissolution and dynamic phase stability in spinel-based lithium-ion battery

Liu, Tongchao; Dai, Alvin; Lu, Jun; Yuan, Yifei; Xiao, Yinguo; Yu, Lei; Li, Matthew; Gim, Jihyeon; Ma, Lu; Liu, Jiajie; Zhan, Chun; Li, Luxi; Zheng, Jiaxin; Ren, Yang; Wu, Tianpin; Shahbazian-Yassar, Reza; Wen, Jianguo; Pan, Feng; Amine, Khalil

doi:10.1038/s41467-019-12626-3

Title: Correlation between manganese dissolution and dynamic phase stability in spinel-based lithium-ion battery

Journal Article · Thu Oct 17 00:00:00 EDT 2019 · Nature Communications

DOI:https://doi.org/10.1038/s41467-019-12626-3· OSTI ID:1607377

Liu, Tongchao ^[1]; Dai, Alvin ^[2];

^[2];

^[3]; Xiao, Yinguo ^[4]; Yu, Lei ^[2]; Li, Matthew ^[2];

^[2];

^[2]; Liu, Jiajie ^[4]; Zhan, Chun ^[2]; Li, Luxi ^[2]; Zheng, Jiaxin ^[4]; Ren, Yang ^[2];

^[2];

^[5];

^[6]; Pan, Feng ^[4];

^[7]

Peking Univ., Shenzhen (China); Argonne National Lab. (ANL), Argonne, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Illinois, Chicago, IL (United States)
Peking Univ., Shenzhen (China)
Univ. of Illinois, Chicago, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
Argonne National Lab. (ANL), Argonne, IL (United States); Stanford Univ., CA (United States); Imam Abdulrahman Bin Faisal Univ. (IAU), Dammam (Saudi Arabia)

Historically long accepted to be the singular root cause of capacity fading, transition metal dissolution has been reported to severely degrade the anode. However, its impact on the cathode behavior remains poorly understood. Here we show the correlation between capacity fading and phase/surface stability of an LiMn₂O₄ cathode. It is revealed that a combination of structural transformation and transition metal dissolution dominates the cathode capacity fading. LiMn₂O₄ exhibits irreversible phase transitions driven by manganese(III) disproportionation and Jahn-Teller distortion, which in conjunction with particle cracks results in serious manganese dissolution. Meanwhile, fast manganese dissolution in turn triggers irreversible structural evolution, and as such, forms a detrimental cycle constantly consuming active cathode components. Furthermore, lithium-rich LiMn₂O₄ with lithium/manganese disorder and surface reconstruction could effectively suppress the irreversible phase transition and manganese dissolution. These findings close the loop of understanding capacity fading mechanisms and allow for development of longer life batteries.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Key Research and Development Program of China; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); National Science Foundation (NSF)

Grant/Contract Number:: AC02-06CH11357; ZDSYS201707281026184

OSTI ID:: 1607377

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: 41 works

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