Design Principles for High-Capacity Mn-Based Cation-Disordered Rocksalt Cathodes
Abstract
Mn-based Li-excess cation-disordered rocksalt (DRX) oxyfluorides are promising candidates for next-generation rechargeable battery cathodes owing to their large energy densities, the earth abundance, and low cost of Mn. In this work, we synthesized and electrochemically tested four representative compositions in the Li-Mn-O-F DRX chemical space with various Li and F content. Although all compositions achieve higher than 200 mAh g-1 initial capacity and good cyclability, we show that the Li-site distribution plays a more important role than the metal-redox capacity in determining the initial capacity, whereas the metal-redox capacity is more closely related to the cyclability of the materials. We apply these insights and generate a capacity map of the Li-Mn-O-F chemical space, LixMn2-xO2-yFy (1.167 ≤ x ≤ 1.333, 0 ≤ y ≤ 0.667), which predicts both accessible Li capacity and Mn-redox capacity. This map provides the design of compounds that balance high capacity with good cyclability.
- Authors:
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); National Science Foundation (NSF)
- OSTI Identifier:
- 1763076
- Alternate Identifier(s):
- OSTI ID: 1594944; OSTI ID: 1609125; OSTI ID: 1702270
- Grant/Contract Number:
- AC02-06CH11357; DEAC02-05CH11231; AC02-05CH11231; ACI1053575; DGE-1106400
- Resource Type:
- Published Article
- Journal Name:
- Chem
- Additional Journal Information:
- Journal Name: Chem Journal Volume: 6 Journal Issue: 1; Journal ID: ISSN 2451-9294
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; cation-disordered rocksalt cathodes; Li-excess Mn-based oxyfluorides; short-range order; density functional theory; Monte Carlo simulation; Li percolation; fluorination; Monte-Carlo simulation
Citation Formats
Lun, Zhengyan, Ouyang, Bin, Cai, Zijian, Clément, Raphaële J., Kwon, Deok-Hwang, Huang, Jianping, Papp, Joseph K., Balasubramanian, Mahalingam, Tian, Yaosen, McCloskey, Bryan D., Ji, Huiwen, Kim, Haegyeom, Kitchaev, Daniil A., and Ceder, Gerbrand. Design Principles for High-Capacity Mn-Based Cation-Disordered Rocksalt Cathodes. United States: N. p., 2020.
Web. doi:10.1016/j.chempr.2019.10.001.
Lun, Zhengyan, Ouyang, Bin, Cai, Zijian, Clément, Raphaële J., Kwon, Deok-Hwang, Huang, Jianping, Papp, Joseph K., Balasubramanian, Mahalingam, Tian, Yaosen, McCloskey, Bryan D., Ji, Huiwen, Kim, Haegyeom, Kitchaev, Daniil A., & Ceder, Gerbrand. Design Principles for High-Capacity Mn-Based Cation-Disordered Rocksalt Cathodes. United States. https://doi.org/10.1016/j.chempr.2019.10.001
Lun, Zhengyan, Ouyang, Bin, Cai, Zijian, Clément, Raphaële J., Kwon, Deok-Hwang, Huang, Jianping, Papp, Joseph K., Balasubramanian, Mahalingam, Tian, Yaosen, McCloskey, Bryan D., Ji, Huiwen, Kim, Haegyeom, Kitchaev, Daniil A., and Ceder, Gerbrand. Wed .
"Design Principles for High-Capacity Mn-Based Cation-Disordered Rocksalt Cathodes". United States. https://doi.org/10.1016/j.chempr.2019.10.001.
@article{osti_1763076,
title = {Design Principles for High-Capacity Mn-Based Cation-Disordered Rocksalt Cathodes},
author = {Lun, Zhengyan and Ouyang, Bin and Cai, Zijian and Clément, Raphaële J. and Kwon, Deok-Hwang and Huang, Jianping and Papp, Joseph K. and Balasubramanian, Mahalingam and Tian, Yaosen and McCloskey, Bryan D. and Ji, Huiwen and Kim, Haegyeom and Kitchaev, Daniil A. and Ceder, Gerbrand},
abstractNote = {Mn-based Li-excess cation-disordered rocksalt (DRX) oxyfluorides are promising candidates for next-generation rechargeable battery cathodes owing to their large energy densities, the earth abundance, and low cost of Mn. In this work, we synthesized and electrochemically tested four representative compositions in the Li-Mn-O-F DRX chemical space with various Li and F content. Although all compositions achieve higher than 200 mAh g-1 initial capacity and good cyclability, we show that the Li-site distribution plays a more important role than the metal-redox capacity in determining the initial capacity, whereas the metal-redox capacity is more closely related to the cyclability of the materials. We apply these insights and generate a capacity map of the Li-Mn-O-F chemical space, LixMn2-xO2-yFy (1.167 ≤ x ≤ 1.333, 0 ≤ y ≤ 0.667), which predicts both accessible Li capacity and Mn-redox capacity. This map provides the design of compounds that balance high capacity with good cyclability.},
doi = {10.1016/j.chempr.2019.10.001},
journal = {Chem},
number = 1,
volume = 6,
place = {United States},
year = {Wed Jan 01 00:00:00 EST 2020},
month = {Wed Jan 01 00:00:00 EST 2020}
}
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Cited by: 60 works
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Figures / Tables:
Figure 1: Structural Characterization of the As-Synthesized Li-Mn-O-F Compounds (A) XRD patterns and refined lattice constants of the as-synthesized materials. (B) Electron diffraction pattern of as-synthesized HLF50. (C) 19F frequency-stepping spectra obtained for the as-synthesized HLF67, HLF50, and LLF67 powders by summing over nine spin-echo sub-spectra acquired at differentmore »
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