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Title: Crystal Chemistry and Electrochemistry of Li xMn 1.5Ni 0.5O 4 Solid Solution Cathode Materials

Abstract

For ordered high-voltage spinel LiMn 1.5Ni 0.5O 4 (LMNO) with the P4 32 1 symmetry, the two consecutive two-phase transformations at ~4.7 V (vs Li +/Li), involving three cubic phases of LMNO, Li 0.5Mn 1.5Ni 0.5O 4 (L 0.5MNO), and Mn 1.5Ni 0.5O 4 (MNO), have been well-established. Such a mechanism is traditionally associated with poor kinetics due to the slow movement of the phase boundaries and the large mechanical strain resulting from the volume changes among the phases, yet ordered LMNO has been shown to have excellent rate capability. In this paper, we show the ability of the phases to dissolve into each other and determine their solubility limit. We characterized the properties of the formed solid solutions and investigated the role of non-equilibrium single-phase redox processes during the charge and discharge of LMNO. Finally, by using an array of advanced analytical techniques, such as soft and hard X-ray spectroscopy, transmission X-ray microscopy, and neutron/X-ray diffraction, as well as bond valence sum analysis, the present study examines the metastable nature of solid-solution phases and provides new insights in enabling cathode materials that are thermodynamically unstable.

Authors:
 [1];  [1];  [2];  [1]; ORCiD logo [3];  [3]; ORCiD logo [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (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)
OSTI Identifier:
1394385
Grant/Contract Number:
AC05-00OR22725; AC02-76SF00515; AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 16; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Kan, Wang Hay, Kuppan, Saravanan, Cheng, Lei, Doeff, Marca, Nanda, Jagjit, Huq, Ashfia, and Chen, Guoying. Crystal Chemistry and Electrochemistry of LixMn1.5Ni0.5O4 Solid Solution Cathode Materials. United States: N. p., 2017. Web. doi:10.1021/acs.chemmater.7b01898.
Kan, Wang Hay, Kuppan, Saravanan, Cheng, Lei, Doeff, Marca, Nanda, Jagjit, Huq, Ashfia, & Chen, Guoying. Crystal Chemistry and Electrochemistry of LixMn1.5Ni0.5O4 Solid Solution Cathode Materials. United States. doi:10.1021/acs.chemmater.7b01898.
Kan, Wang Hay, Kuppan, Saravanan, Cheng, Lei, Doeff, Marca, Nanda, Jagjit, Huq, Ashfia, and Chen, Guoying. 2017. "Crystal Chemistry and Electrochemistry of LixMn1.5Ni0.5O4 Solid Solution Cathode Materials". United States. doi:10.1021/acs.chemmater.7b01898.
@article{osti_1394385,
title = {Crystal Chemistry and Electrochemistry of LixMn1.5Ni0.5O4 Solid Solution Cathode Materials},
author = {Kan, Wang Hay and Kuppan, Saravanan and Cheng, Lei and Doeff, Marca and Nanda, Jagjit and Huq, Ashfia and Chen, Guoying},
abstractNote = {For ordered high-voltage spinel LiMn1.5Ni0.5O4 (LMNO) with the P4321 symmetry, the two consecutive two-phase transformations at ~4.7 V (vs Li+/Li), involving three cubic phases of LMNO, Li0.5Mn1.5Ni0.5O4 (L0.5MNO), and Mn1.5Ni0.5O4 (MNO), have been well-established. Such a mechanism is traditionally associated with poor kinetics due to the slow movement of the phase boundaries and the large mechanical strain resulting from the volume changes among the phases, yet ordered LMNO has been shown to have excellent rate capability. In this paper, we show the ability of the phases to dissolve into each other and determine their solubility limit. We characterized the properties of the formed solid solutions and investigated the role of non-equilibrium single-phase redox processes during the charge and discharge of LMNO. Finally, by using an array of advanced analytical techniques, such as soft and hard X-ray spectroscopy, transmission X-ray microscopy, and neutron/X-ray diffraction, as well as bond valence sum analysis, the present study examines the metastable nature of solid-solution phases and provides new insights in enabling cathode materials that are thermodynamically unstable.},
doi = {10.1021/acs.chemmater.7b01898},
journal = {Chemistry of Materials},
number = 16,
volume = 29,
place = {United States},
year = 2017,
month = 7
}

Journal Article:
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