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Title: Ultrahigh power and energy density in partially ordered lithium-ion cathode materials

Abstract

There is an intensive search for high-performance cathode materials for rechargeable batteries. In this work the authors report that oxyfluorides with partial spinel-like cation order, made from earth-abundant elements, display both exceptionally high energy and power. The rapid market growth of rechargeable batteries requires electrode materials that combine high power and energy and are made from earth-abundant elements. In this paper we show that combining a partial spinel-like cation order and substantial lithium excess enables both dense and fast energy storage. Cation overstoichiometry and the resulting partial order is used to eliminate the phase transitions typical of ordered spinels and enable a larger practical capacity, while lithium excess is synergistically used with fluorine substitution to create a high lithium mobility. With this strategy, we achieved specific energies greater than 1,100 Wh kg-1 and discharge rates up to 20 A g-1. Remarkably, the cathode materials thus obtained from inexpensive manganese present a rare case wherein an excellent rate capability coexists with a reversible oxygen redox activity. Our work shows the potential for designing cathode materials in the vast space between fully ordered and disordered compounds.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1]; ORCiD logo [3];  [1]; ORCiD logo [4]; ORCiD logo [5];  [6];  [7]; ORCiD logo [1];  [8]; ORCiD logo [4];  [7]; ORCiD logo [9]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  5. Columbia Univ., New York, NY (United States)
  6. Univ. of California, Berkeley, CA (United States)
  7. Univ. of California, Santa Barbara, CA (United States)
  8. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  9. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS) and The Molecular Foundry (TMF)
Sponsoring Org.:
Umicore Specialty Oxides and Chemicals; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Science Foundation (NSF)
OSTI Identifier:
1633083
Alternate Identifier(s):
OSTI ID: 1634077
Grant/Contract Number:  
AC02-06CH11357; AC02-05CH11231; DGE-1106400
Resource Type:
Accepted Manuscript
Journal Name:
Nature Energy
Additional Journal Information:
Journal Volume: 5; Journal Issue: 3; Journal ID: ISSN 2058-7546
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Batteries; Energy storage; Materials for energy and catalysis

Citation Formats

Ji, Huiwen, Wu, Jinpeng, Cai, Zijian, Liu, Jue, Kwon, Deok-Hwang, Kim, Hyunchul, Urban, Alexander, Papp, Joseph K., Foley, Emily, Tian, Yaosen, Balasubramanian, Mahalingam, Kim, Haegyeom, Clément, Raphaële J., McCloskey, Bryan D., Yang, Wanli, and Ceder, Gerbrand. Ultrahigh power and energy density in partially ordered lithium-ion cathode materials. United States: N. p., 2020. Web. doi:10.1038/s41560-020-0573-1.
Ji, Huiwen, Wu, Jinpeng, Cai, Zijian, Liu, Jue, Kwon, Deok-Hwang, Kim, Hyunchul, Urban, Alexander, Papp, Joseph K., Foley, Emily, Tian, Yaosen, Balasubramanian, Mahalingam, Kim, Haegyeom, Clément, Raphaële J., McCloskey, Bryan D., Yang, Wanli, & Ceder, Gerbrand. Ultrahigh power and energy density in partially ordered lithium-ion cathode materials. United States. doi:https://doi.org/10.1038/s41560-020-0573-1
Ji, Huiwen, Wu, Jinpeng, Cai, Zijian, Liu, Jue, Kwon, Deok-Hwang, Kim, Hyunchul, Urban, Alexander, Papp, Joseph K., Foley, Emily, Tian, Yaosen, Balasubramanian, Mahalingam, Kim, Haegyeom, Clément, Raphaële J., McCloskey, Bryan D., Yang, Wanli, and Ceder, Gerbrand. Mon . "Ultrahigh power and energy density in partially ordered lithium-ion cathode materials". United States. doi:https://doi.org/10.1038/s41560-020-0573-1. https://www.osti.gov/servlets/purl/1633083.
@article{osti_1633083,
title = {Ultrahigh power and energy density in partially ordered lithium-ion cathode materials},
author = {Ji, Huiwen and Wu, Jinpeng and Cai, Zijian and Liu, Jue and Kwon, Deok-Hwang and Kim, Hyunchul and Urban, Alexander and Papp, Joseph K. and Foley, Emily and Tian, Yaosen and Balasubramanian, Mahalingam and Kim, Haegyeom and Clément, Raphaële J. and McCloskey, Bryan D. and Yang, Wanli and Ceder, Gerbrand},
abstractNote = {There is an intensive search for high-performance cathode materials for rechargeable batteries. In this work the authors report that oxyfluorides with partial spinel-like cation order, made from earth-abundant elements, display both exceptionally high energy and power. The rapid market growth of rechargeable batteries requires electrode materials that combine high power and energy and are made from earth-abundant elements. In this paper we show that combining a partial spinel-like cation order and substantial lithium excess enables both dense and fast energy storage. Cation overstoichiometry and the resulting partial order is used to eliminate the phase transitions typical of ordered spinels and enable a larger practical capacity, while lithium excess is synergistically used with fluorine substitution to create a high lithium mobility. With this strategy, we achieved specific energies greater than 1,100 Wh kg-1 and discharge rates up to 20 A g-1. Remarkably, the cathode materials thus obtained from inexpensive manganese present a rare case wherein an excellent rate capability coexists with a reversible oxygen redox activity. Our work shows the potential for designing cathode materials in the vast space between fully ordered and disordered compounds.},
doi = {10.1038/s41560-020-0573-1},
journal = {Nature Energy},
number = 3,
volume = 5,
place = {United States},
year = {2020},
month = {3}
}

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