Structural and Chemical Evolution of Li- and Mn-rich Layered Cathode Material

Zheng, Jianming; Xu, Pinghong; Gu, Meng; Xiao, Jie; Browning, Nigel D.; Yan, Pengfei; Wang, Chong M.; Zhang, Jiguang

doi:10.1021/cm5045978

Title: Structural and Chemical Evolution of Li- and Mn-rich Layered Cathode Material

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Abstract

Lithium (Li)- and manganese-rich (LMR) layered-structure materials are very promising cathodes for high energy density lithium-ion batteries. However, their voltage fading mechanism and its relationships with fundamental structural changes are far from being sufficiently understood. Here we report the detailed phase transformation pathway in the LMR cathode (Li[Li0.2Ni0.2Mn0.6]O2) during cycling for the samples prepared by hydro-thermal assistant method. It is found the transformation pathway of LMR cathode is closely correlated to its initial structure and preparation conditions. The results reveal that LMR cathode prepared by HA approach experiences a phase transformation from the layered structure to a LT-LiCoO2 type defect spinel-like structure (Fd-3m space group) and then to a disordered rock-salt structure (Fm-3m space group). The voltage fade can be well correlated with the Li ion insertion into octahedral sites, rather than tetrahedral sites, in both defect spinel-like structure and disordered rock-salt structure. The reversible Li insertion/removal into/from the disordered rock-salt structure is ascribed to the Li excess environment that can satisfy the Li percolating in the disordered rock-salt structure despite the increased kinetic barrier. Meanwhile, because of the presence of a great amount of oxygen vacancies, a significant decrease of Mn valence is detected in the cycled particle, whichmore »« less

Authors:: Zheng, Jianming; Xu, Pinghong; Gu, Meng; Xiao, Jie; Browning, Nigel D.; Yan, Pengfei; Wang, Chong M.; Zhang, Jiguang

Publication Date:: Tue Feb 24 00:00:00 EST 2015

Research Org.:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1208781

Report Number(s):: PNNL-SA-107139
48164; VT1201000

DOE Contract Number:: AC05-76RL01830

Resource Type:: Journal Article

Journal Name:: Chemistry of Materials, 27(4):1381-1390

Additional Journal Information:: Journal Name: Chemistry of Materials, 27(4):1381-1390

Country of Publication:: United States

Language:: English

Subject:: Layered structure; Spinel formation; Rock-salt structure; Cation redistribution; Voltage fade; Li ion battery; Environmental Molecular Sciences Laboratory

Citation Formats


                    Zheng, Jianming, Xu, Pinghong, Gu, Meng, Xiao, Jie, Browning, Nigel D., Yan, Pengfei, Wang, Chong M., and Zhang, Jiguang. Structural and Chemical Evolution of Li- and Mn-rich Layered Cathode Material.  United States: N. p., 2015. 
        Web.  doi:10.1021/cm5045978.

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                    Zheng, Jianming, Xu, Pinghong, Gu, Meng, Xiao, Jie, Browning, Nigel D., Yan, Pengfei, Wang, Chong M., & Zhang, Jiguang. Structural and Chemical Evolution of Li- and Mn-rich Layered Cathode Material.  United States.  https://doi.org/10.1021/cm5045978

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                    Zheng, Jianming, Xu, Pinghong, Gu, Meng, Xiao, Jie, Browning, Nigel D., Yan, Pengfei, Wang, Chong M., and Zhang, Jiguang. 2015.  
        "Structural and Chemical Evolution of Li- and Mn-rich Layered Cathode Material".  United States.  https://doi.org/10.1021/cm5045978.

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@article{osti_1208781,

  title        = {Structural and Chemical Evolution of Li- and Mn-rich Layered Cathode Material},

  author       = {Zheng, Jianming and Xu, Pinghong and Gu, Meng and Xiao, Jie and Browning, Nigel D. and Yan, Pengfei and Wang, Chong M. and Zhang, Jiguang},

  abstractNote = {Lithium (Li)- and manganese-rich (LMR) layered-structure materials are very promising cathodes for high energy density lithium-ion batteries. However, their voltage fading mechanism and its relationships with fundamental structural changes are far from being sufficiently understood. Here we report the detailed phase transformation pathway in the LMR cathode (Li[Li0.2Ni0.2Mn0.6]O2) during cycling for the samples prepared by hydro-thermal assistant method. It is found the transformation pathway of LMR cathode is closely correlated to its initial structure and preparation conditions. The results reveal that LMR cathode prepared by HA approach experiences a phase transformation from the layered structure to a LT-LiCoO2 type defect spinel-like structure (Fd-3m space group) and then to a disordered rock-salt structure (Fm-3m space group). The voltage fade can be well correlated with the Li ion insertion into octahedral sites, rather than tetrahedral sites, in both defect spinel-like structure and disordered rock-salt structure. The reversible Li insertion/removal into/from the disordered rock-salt structure is ascribed to the Li excess environment that can satisfy the Li percolating in the disordered rock-salt structure despite the increased kinetic barrier. Meanwhile, because of the presence of a great amount of oxygen vacancies, a significant decrease of Mn valence is detected in the cycled particle, which is below that anticipated for a potentially damaging Jahn-Teller distortion (+3.5). Clarification of the phase transformation pathway, cation redistribution, oxygen vacancy and Mn valence change undoubtedly provides insights into a profound understanding on the voltage fade, and capacity degradation of LMR cathode. The results also inspire us to further enhance the reversibility of LMR cathode via improving its surface structural stability.},

  doi          = {10.1021/cm5045978},

  url          = {https://www.osti.gov/biblio/1208781},
  journal      = {Chemistry of Materials, 27(4):1381-1390},
number       = ,

  volume       = ,

  place        = {United States},

  year         = {Tue Feb 24 00:00:00 EST 2015},

  month        = {Tue Feb 24 00:00:00 EST 2015}

}

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