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Title: Reversible Mn 2+/Mn 4+ double redox in lithium-excess cathode materials

There is an urgent need for low-cost, resource-friendly, high-energy-density cathode materials for lithium-ion batteries to satisfy the rapidly increasing need for electrical energy storage. To replace the nickel and cobalt, which are limited resources and are associated with safety problems, in current lithium-ion batteries, high-capacity cathodes based on manganese would be particularly desirable owing to the low cost and high abundance of the metal, and the intrinsic stability of the Mn 4+ oxidation state. In this paper we present a strategy of combining high-valent cations and the partial substitution of fluorine for oxygen in a disordered-rocksalt structure to incorporate the reversible Mn 2+/Mn 4+ double redox couple into lithium-excess cathode materials. The lithium-rich cathodes thus produced have high capacity and energy density. Finally, the use of the Mn 2+/Mn 4+ redox reduces oxygen redox activity, thereby stabilizing the materials, and opens up new opportunities for the design of high-performance manganese-rich cathodes for advanced lithium-ion batteries.
Authors:
 [1] ;  [2] ;  [1] ;  [3] ;  [4] ;  [5] ;  [1] ;  [1] ;  [1] ;  [6] ;  [7] ;  [3] ;  [8]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering
  2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering
  3. Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division. Advanced Photon Source
  4. Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source
  6. Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Storage and Distributed Resources Division
  7. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source; Univ. of California, Santa Cruz, CA (United States). Dept. of Chemistry and Biochemistry
  8. Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Science Division
Publication Date:
Grant/Contract Number:
AC02-06CH11357; AC02-05CH11231; ACI-1548562; DGE-1106400; DMR-1720256
Type:
Accepted Manuscript
Journal Name:
Nature (London)
Additional Journal Information:
Journal Name: Nature (London); Journal Volume: 556; Journal Issue: 7700; Journal ID: ISSN 0028-0836
Publisher:
Nature Publishing Group
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (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); National Science Foundation (NSF)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; atomistic models; batteries
OSTI Identifier:
1461423

Lee, Jinhyuk, Kitchaev, Daniil A., Kwon, Deok-Hwang, Lee, Chang-Wook, Papp, Joseph K., Liu, Yi-Sheng, Lun, Zhengyan, Clement, Raphaele J., Shi, Tan, McCloskey, Bryan D., Guo, Jinghua, Balasubramanian, Mahalingam, and Ceder, Gerbrand. Reversible Mn2+/Mn4+ double redox in lithium-excess cathode materials. United States: N. p., Web. doi:10.1038/s41586-018-0015-4.
Lee, Jinhyuk, Kitchaev, Daniil A., Kwon, Deok-Hwang, Lee, Chang-Wook, Papp, Joseph K., Liu, Yi-Sheng, Lun, Zhengyan, Clement, Raphaele J., Shi, Tan, McCloskey, Bryan D., Guo, Jinghua, Balasubramanian, Mahalingam, & Ceder, Gerbrand. Reversible Mn2+/Mn4+ double redox in lithium-excess cathode materials. United States. doi:10.1038/s41586-018-0015-4.
Lee, Jinhyuk, Kitchaev, Daniil A., Kwon, Deok-Hwang, Lee, Chang-Wook, Papp, Joseph K., Liu, Yi-Sheng, Lun, Zhengyan, Clement, Raphaele J., Shi, Tan, McCloskey, Bryan D., Guo, Jinghua, Balasubramanian, Mahalingam, and Ceder, Gerbrand. 2018. "Reversible Mn2+/Mn4+ double redox in lithium-excess cathode materials". United States. doi:10.1038/s41586-018-0015-4.
@article{osti_1461423,
title = {Reversible Mn2+/Mn4+ double redox in lithium-excess cathode materials},
author = {Lee, Jinhyuk and Kitchaev, Daniil A. and Kwon, Deok-Hwang and Lee, Chang-Wook and Papp, Joseph K. and Liu, Yi-Sheng and Lun, Zhengyan and Clement, Raphaele J. and Shi, Tan and McCloskey, Bryan D. and Guo, Jinghua and Balasubramanian, Mahalingam and Ceder, Gerbrand},
abstractNote = {There is an urgent need for low-cost, resource-friendly, high-energy-density cathode materials for lithium-ion batteries to satisfy the rapidly increasing need for electrical energy storage. To replace the nickel and cobalt, which are limited resources and are associated with safety problems, in current lithium-ion batteries, high-capacity cathodes based on manganese would be particularly desirable owing to the low cost and high abundance of the metal, and the intrinsic stability of the Mn4+ oxidation state. In this paper we present a strategy of combining high-valent cations and the partial substitution of fluorine for oxygen in a disordered-rocksalt structure to incorporate the reversible Mn2+/Mn4+ double redox couple into lithium-excess cathode materials. The lithium-rich cathodes thus produced have high capacity and energy density. Finally, the use of the Mn2+/Mn4+ redox reduces oxygen redox activity, thereby stabilizing the materials, and opens up new opportunities for the design of high-performance manganese-rich cathodes for advanced lithium-ion batteries.},
doi = {10.1038/s41586-018-0015-4},
journal = {Nature (London)},
number = 7700,
volume = 556,
place = {United States},
year = {2018},
month = {4}
}

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