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Title: Improved Cycling Performance of Li-Excess Cation-Disordered Cathode Materials upon Fluorine Substitution

Abstract

We report the recent discovery of Li-excess cation-disordered rock salt cathodes has greatly enlarged the design space of Li-ion cathode materials. Evidence of facile lattice fluorine substitution for oxygen has further provided an important strategy to enhance the cycling performance of this class of materials. Here, a group of Mn 3+–Nb 5+-based cation-disordered oxyfluorides, Li 1.2Mn 3+ 0.6+0.5xNb 5+ 0.2-0.5xO 2-xF x (x = 0, 0.05, 0.1, 0.15, 0.2) is investigated and it is found that fluorination improves capacity retention in a very significant way. Combining spectroscopic methods and ab initio calculations, it is demonstrated that the increased transition-metal redox (Mn 3+/Mn 4+) capacity that can be accommodated upon fluorination reduces reliance on oxygen redox and leads to less oxygen loss, as evidenced by differential electrochemical mass spectroscopy measurements. Furthermore, it is found that fluorine substitution also decreases the Mn 3+-induced Jahn–Teller distortion, leading to an orbital rearrangement that further increases the contribution of Mn-redox capacity to the overall capacity.

Authors:
 [1];  [1];  [2];  [3];  [4];  [5];  [3];  [4];  [1];  [6];  [3]; ORCiD logo [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  4. Univ. of California, Berkeley, CA (United States)
  5. Argonne National Lab. (ANL), Argonne, IL (United States)
  6. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Robert Bosch GmbH; Umicore
OSTI Identifier:
1493873
Alternate Identifier(s):
OSTI ID: 1482427
Grant/Contract Number:  
AC02-06CH11357; AC02‐05CH11231; AC02-05CH11231; NSF DMR 1720256
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 9; Journal Issue: 2; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; cyclability; DFT; fluorination; Jahn–Teller distortion; Li‐excess cation‐disordered cathodes

Citation Formats

Lun, Zhengyan, Ouyang, Bin, Kitchaev, Daniil A., Clément, Raphaële J., Papp, Joseph K., Balasubramanian, Mahalingam, Tian, Yaosen, Lei, Teng, Shi, Tan, McCloskey, Bryan D., Lee, Jinhyuk, and Ceder, Gerbrand. Improved Cycling Performance of Li-Excess Cation-Disordered Cathode Materials upon Fluorine Substitution. United States: N. p., 2018. Web. doi:10.1002/aenm.201802959.
Lun, Zhengyan, Ouyang, Bin, Kitchaev, Daniil A., Clément, Raphaële J., Papp, Joseph K., Balasubramanian, Mahalingam, Tian, Yaosen, Lei, Teng, Shi, Tan, McCloskey, Bryan D., Lee, Jinhyuk, & Ceder, Gerbrand. Improved Cycling Performance of Li-Excess Cation-Disordered Cathode Materials upon Fluorine Substitution. United States. doi:10.1002/aenm.201802959.
Lun, Zhengyan, Ouyang, Bin, Kitchaev, Daniil A., Clément, Raphaële J., Papp, Joseph K., Balasubramanian, Mahalingam, Tian, Yaosen, Lei, Teng, Shi, Tan, McCloskey, Bryan D., Lee, Jinhyuk, and Ceder, Gerbrand. Fri . "Improved Cycling Performance of Li-Excess Cation-Disordered Cathode Materials upon Fluorine Substitution". United States. doi:10.1002/aenm.201802959.
@article{osti_1493873,
title = {Improved Cycling Performance of Li-Excess Cation-Disordered Cathode Materials upon Fluorine Substitution},
author = {Lun, Zhengyan and Ouyang, Bin and Kitchaev, Daniil A. and Clément, Raphaële J. and Papp, Joseph K. and Balasubramanian, Mahalingam and Tian, Yaosen and Lei, Teng and Shi, Tan and McCloskey, Bryan D. and Lee, Jinhyuk and Ceder, Gerbrand},
abstractNote = {We report the recent discovery of Li-excess cation-disordered rock salt cathodes has greatly enlarged the design space of Li-ion cathode materials. Evidence of facile lattice fluorine substitution for oxygen has further provided an important strategy to enhance the cycling performance of this class of materials. Here, a group of Mn3+–Nb5+-based cation-disordered oxyfluorides, Li1.2Mn3+0.6+0.5xNb5+0.2-0.5xO2-xFx (x = 0, 0.05, 0.1, 0.15, 0.2) is investigated and it is found that fluorination improves capacity retention in a very significant way. Combining spectroscopic methods and ab initio calculations, it is demonstrated that the increased transition-metal redox (Mn3+/Mn4+) capacity that can be accommodated upon fluorination reduces reliance on oxygen redox and leads to less oxygen loss, as evidenced by differential electrochemical mass spectroscopy measurements. Furthermore, it is found that fluorine substitution also decreases the Mn3+-induced Jahn–Teller distortion, leading to an orbital rearrangement that further increases the contribution of Mn-redox capacity to the overall capacity.},
doi = {10.1002/aenm.201802959},
journal = {Advanced Energy Materials},
number = 2,
volume = 9,
place = {United States},
year = {2018},
month = {11}
}

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