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Title: Design principles for high transition metal capacity in disordered rocksalt Li-ion cathodes

Here, the discovery of facile Li transport in disordered, Li-excess rocksalt materials has opened a vast new chemical space for the development of high energy density, low cost Li-ion cathodes. We develop a strategy for obtaining optimized compositions within this class of materials, exhibiting high capacity and energy density as well as good reversibility, by using a combination of low-valence transition metal redox and a high-valence redox active charge compensator, as well as fluorine substitution for oxygen. Furthermore, we identify a new constraint on high-performance compositions by demonstrating the necessity of excess Li capacity as a means of counteracting high-voltage tetrahedral Li formation, Li-binding by fluorine and the associated irreversibility. Specifically, we demonstrate that 10–12% of Li capacity is lost due to tetrahedral Li formation, and 0.4–0.8 Li per F dopant is made inaccessible at moderate voltages due to Li–F binding. We demonstrate the success of this strategy by realizing a series of high-performance disordered oxyfluoride cathode materials based on Mn 2+/4+ and V 4+/5+ redox.
Authors:
ORCiD logo [1] ; ORCiD logo [2] ;  [1] ;  [2] ; ORCiD logo [3] ; ORCiD logo [4] ;  [5] ;  [5] ;  [3] ;  [3] ;  [3] ; ORCiD logo [5] ;  [3] ;  [6]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  3. Univ. of California, Berkeley, CA (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  6. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357; AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Energy & Environmental Science
Additional Journal Information:
Journal Volume: 11; Journal Issue: 8; Journal ID: ISSN 1754-5692
Publisher:
Royal Society of Chemistry
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE
OSTI Identifier:
1471056
Alternate Identifier(s):
OSTI ID: 1477348

Kitchaev, Daniil A., Lun, Zhengyan, Richards, William D., Ji, Huiwen, Clément, Raphaële J., Balasubramanian, Mahalingam, Kwon, Deok -Hwang, Dai, Kehua, Papp, Joseph K., Lei, Teng, McCloskey, Bryan D., Yang, Wanli, Lee, Jinhyuk, and Ceder, Gerbrand. Design principles for high transition metal capacity in disordered rocksalt Li-ion cathodes. United States: N. p., Web. doi:10.1039/c8ee00816g.
Kitchaev, Daniil A., Lun, Zhengyan, Richards, William D., Ji, Huiwen, Clément, Raphaële J., Balasubramanian, Mahalingam, Kwon, Deok -Hwang, Dai, Kehua, Papp, Joseph K., Lei, Teng, McCloskey, Bryan D., Yang, Wanli, Lee, Jinhyuk, & Ceder, Gerbrand. Design principles for high transition metal capacity in disordered rocksalt Li-ion cathodes. United States. doi:10.1039/c8ee00816g.
Kitchaev, Daniil A., Lun, Zhengyan, Richards, William D., Ji, Huiwen, Clément, Raphaële J., Balasubramanian, Mahalingam, Kwon, Deok -Hwang, Dai, Kehua, Papp, Joseph K., Lei, Teng, McCloskey, Bryan D., Yang, Wanli, Lee, Jinhyuk, and Ceder, Gerbrand. 2018. "Design principles for high transition metal capacity in disordered rocksalt Li-ion cathodes". United States. doi:10.1039/c8ee00816g. https://www.osti.gov/servlets/purl/1471056.
@article{osti_1471056,
title = {Design principles for high transition metal capacity in disordered rocksalt Li-ion cathodes},
author = {Kitchaev, Daniil A. and Lun, Zhengyan and Richards, William D. and Ji, Huiwen and Clément, Raphaële J. and Balasubramanian, Mahalingam and Kwon, Deok -Hwang and Dai, Kehua and Papp, Joseph K. and Lei, Teng and McCloskey, Bryan D. and Yang, Wanli and Lee, Jinhyuk and Ceder, Gerbrand},
abstractNote = {Here, the discovery of facile Li transport in disordered, Li-excess rocksalt materials has opened a vast new chemical space for the development of high energy density, low cost Li-ion cathodes. We develop a strategy for obtaining optimized compositions within this class of materials, exhibiting high capacity and energy density as well as good reversibility, by using a combination of low-valence transition metal redox and a high-valence redox active charge compensator, as well as fluorine substitution for oxygen. Furthermore, we identify a new constraint on high-performance compositions by demonstrating the necessity of excess Li capacity as a means of counteracting high-voltage tetrahedral Li formation, Li-binding by fluorine and the associated irreversibility. Specifically, we demonstrate that 10–12% of Li capacity is lost due to tetrahedral Li formation, and 0.4–0.8 Li per F dopant is made inaccessible at moderate voltages due to Li–F binding. We demonstrate the success of this strategy by realizing a series of high-performance disordered oxyfluoride cathode materials based on Mn2+/4+ and V4+/5+ redox.},
doi = {10.1039/c8ee00816g},
journal = {Energy & Environmental Science},
number = 8,
volume = 11,
place = {United States},
year = {2018},
month = {5}
}

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