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Title: Identification of ferrimagnetic orbitals preventing spinel degradation by charge ordering in LixMn2O4

Abstract

Spinel Lix Mn2 O4 is a key cathode material that is used extensively in commercial Li-ion batteries. A challenge with this material has been that the capacity of the battery fades with cycling, an effect that can be traced to the presence of an antiferromagnetic insulator phase in the fully lithiated LiMn2O4 (LMO) and the associated charge disproportionation that drives distortions of the MnO6 octahedra. Here, by combining x-ray magnetic Compton scattering experiments with parallel first-principles computations, we show that the antiferromagnetic phase of LMO is surrounded by a robust ferrimagnetic metallic phase, which becomes stable when even a small amount of Li is removed from or added to the charge-ordered LMO. In this surprising ferrimagnetic state, charge-ordering and octahedral distortions are found to be strongly suppressed. We identify the nature of the ferrimagnetic orbitals involved through theoretical and experimental analyses of the magnetic Compton scattering spectra.

Authors:
ORCiD logo [1];  [2];  [3];  [4];  [5];  [6];  [7];  [2];  [2];  [7];  [6];  [2];  [1]
+ Show Author Affiliations
  1. Northeastern Univ., Boston, MA (United States)
  2. Gunma Univ. (Japan)
  3. Northeastern Univ., Boston, MA (United States); LUT Univ., Lappeenranta (Finland)
  4. Ritsumeikan Univ., Kusatsu, Shiga (Japan)
  5. Northeastern Univ., Boston, MA (United States); AGH - Univ. of Science and Technology, Krakow (Poland)
  6. Japan Synchrotron Radiation Research Inst. (Japan)
  7. Kyoto Univ. (Japan)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Complex Materials from First Principles (CCM); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States); Northeastern Univ., Boston, MA (United States); Temple Univ., Philadelphia, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1577815
Grant/Contract Number:  
AC02-05CH11231; FG02-07ER46352; SC0012575
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review. B
Additional Journal Information:
Journal Volume: 100; Journal Issue: 20; Journal ID: ISSN 2469-9950
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; Materials Science; Physics; ChargeDensity of states; Electronic structure; Jahn-Teller effect; Magnetic phase transitions; Magnetism; Antiferromagnets; Energy applications; Energy materials; Ferrimagnets; Functional materials; Density functional theory; First-principles calculations; Hubbard model; X-ray scattering; X-ray techniques

Citation Formats

Hafiz, Hasnain, Suzuki, Kosuke, Barbiellini, Bernardo, Orikasa, Yuki, Kaprzyk, Stanislaw, Tsuji, Naruki, Yamamoto, Kentaro, Terasaka, Ayumu, Hoshi, Kazushi, Uchimoto, Yoshiharu, Sakurai, Yoshiharu, Sakurai, Hiroshi, and Bansil, Arun. Identification of ferrimagnetic orbitals preventing spinel degradation by charge ordering in LixMn2O4. United States: N. p., 2019. Web. doi:10.1103/physrevb.100.205104.
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Hafiz, Hasnain, Suzuki, Kosuke, Barbiellini, Bernardo, Orikasa, Yuki, Kaprzyk, Stanislaw, Tsuji, Naruki, Yamamoto, Kentaro, Terasaka, Ayumu, Hoshi, Kazushi, Uchimoto, Yoshiharu, Sakurai, Yoshiharu, Sakurai, Hiroshi, & Bansil, Arun. Identification of ferrimagnetic orbitals preventing spinel degradation by charge ordering in LixMn2O4. United States. https://doi.org/10.1103/physrevb.100.205104
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Hafiz, Hasnain, Suzuki, Kosuke, Barbiellini, Bernardo, Orikasa, Yuki, Kaprzyk, Stanislaw, Tsuji, Naruki, Yamamoto, Kentaro, Terasaka, Ayumu, Hoshi, Kazushi, Uchimoto, Yoshiharu, Sakurai, Yoshiharu, Sakurai, Hiroshi, and Bansil, Arun. Mon . "Identification of ferrimagnetic orbitals preventing spinel degradation by charge ordering in LixMn2O4". United States. https://doi.org/10.1103/physrevb.100.205104. https://www.osti.gov/servlets/purl/1577815.
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@article{osti_1577815,
title = {Identification of ferrimagnetic orbitals preventing spinel degradation by charge ordering in LixMn2O4},
author = {Hafiz, Hasnain and Suzuki, Kosuke and Barbiellini, Bernardo and Orikasa, Yuki and Kaprzyk, Stanislaw and Tsuji, Naruki and Yamamoto, Kentaro and Terasaka, Ayumu and Hoshi, Kazushi and Uchimoto, Yoshiharu and Sakurai, Yoshiharu and Sakurai, Hiroshi and Bansil, Arun},
abstractNote = {Spinel Lix Mn2 O4 is a key cathode material that is used extensively in commercial Li-ion batteries. A challenge with this material has been that the capacity of the battery fades with cycling, an effect that can be traced to the presence of an antiferromagnetic insulator phase in the fully lithiated LiMn2O4 (LMO) and the associated charge disproportionation that drives distortions of the MnO6 octahedra. Here, by combining x-ray magnetic Compton scattering experiments with parallel first-principles computations, we show that the antiferromagnetic phase of LMO is surrounded by a robust ferrimagnetic metallic phase, which becomes stable when even a small amount of Li is removed from or added to the charge-ordered LMO. In this surprising ferrimagnetic state, charge-ordering and octahedral distortions are found to be strongly suppressed. We identify the nature of the ferrimagnetic orbitals involved through theoretical and experimental analyses of the magnetic Compton scattering spectra.},
doi = {10.1103/physrevb.100.205104},
journal = {Physical Review. B},
number = 20,
volume = 100,
place = {United States},
year = {Mon Nov 04 00:00:00 EST 2019},
month = {Mon Nov 04 00:00:00 EST 2019}
}
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https://doi.org/10.1103/physrevb.100.205104
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