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Title: Long-Term Cycling of a Mn-Rich High-Voltage Spinel Cathode by Stabilizing the Surface with a Small Dose of Iron

Abstract

The high-voltage, cobalt-free spinel cathode LiNi0.5Mn1.5O4 (LNMO) is receiving extensive attention for lithium-ion batteries due to its low cost, high operating voltage and energy density, superior power density, and good thermal stability. However, its high operating voltage hampers its stability with commercial electrolytes and makes its practical viability challenging. We present here a Mn-rich LNMO cathode to encourage the disordering of Mn and Ni in the lattice and the incorporation of a small dose of Fe into Mn-rich LNMO (Fe-LNMO) to improve the cycling stability. The introduction of Fe further increases the cation disorder between Mn and Ni, thus enabling a better rate capability. Electron energy loss spectroscopy analysis indicates that Fe is concentrated on the surface, and X-ray photoelectron spectroscopy analysis shows that Fe-LNMO alleviates the aggressive reaction between the cathode surface and the electrolyte, thus stabilizing the interface and cycle life. Furthermore, a full cell assembled with a graphite anode with an areal capacity of 3 mA h cm–2 displays a capacity retention of 90% over 300 cycles. Furthermore, the present work demonstrates an effective way to promote cation disordering and lower the surface reactivity of LNMO with the electrolyte, thereby enhancing the conductivity, stabilizing the cathode–electrolyte interphase,more » and making LNMO promising for practical applications.« less

Authors:
 [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
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  1. Univ. of Texas, Austin, TX (United States)
Publication Date:
Research Org.:
Univ. of California, San Diego, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1969519
Grant/Contract Number:  
EE0008442
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Energy Materials
Additional Journal Information:
Journal Volume: 4; Journal Issue: 11; Journal ID: ISSN 2574-0962
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; high-voltage spinel; cation disorder; Fe-rich surface; interface reaction; cycling stability; electrochemical cells; electrodes; electrolytes; metals; transition metals

Citation Formats

Zou, Feng, Cui, Zehao, Nallan, Himamshu C., Ekerdt, John G., and Manthiram, Arumugam. Long-Term Cycling of a Mn-Rich High-Voltage Spinel Cathode by Stabilizing the Surface with a Small Dose of Iron. United States: N. p., 2021. Web. doi:10.1021/acsaem.1c02903.
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Zou, Feng, Cui, Zehao, Nallan, Himamshu C., Ekerdt, John G., & Manthiram, Arumugam. Long-Term Cycling of a Mn-Rich High-Voltage Spinel Cathode by Stabilizing the Surface with a Small Dose of Iron. United States. https://doi.org/10.1021/acsaem.1c02903
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Zou, Feng, Cui, Zehao, Nallan, Himamshu C., Ekerdt, John G., and Manthiram, Arumugam. Thu . "Long-Term Cycling of a Mn-Rich High-Voltage Spinel Cathode by Stabilizing the Surface with a Small Dose of Iron". United States. https://doi.org/10.1021/acsaem.1c02903. https://www.osti.gov/servlets/purl/1969519.
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@article{osti_1969519,
title = {Long-Term Cycling of a Mn-Rich High-Voltage Spinel Cathode by Stabilizing the Surface with a Small Dose of Iron},
author = {Zou, Feng and Cui, Zehao and Nallan, Himamshu C. and Ekerdt, John G. and Manthiram, Arumugam},
abstractNote = {The high-voltage, cobalt-free spinel cathode LiNi0.5Mn1.5O4 (LNMO) is receiving extensive attention for lithium-ion batteries due to its low cost, high operating voltage and energy density, superior power density, and good thermal stability. However, its high operating voltage hampers its stability with commercial electrolytes and makes its practical viability challenging. We present here a Mn-rich LNMO cathode to encourage the disordering of Mn and Ni in the lattice and the incorporation of a small dose of Fe into Mn-rich LNMO (Fe-LNMO) to improve the cycling stability. The introduction of Fe further increases the cation disorder between Mn and Ni, thus enabling a better rate capability. Electron energy loss spectroscopy analysis indicates that Fe is concentrated on the surface, and X-ray photoelectron spectroscopy analysis shows that Fe-LNMO alleviates the aggressive reaction between the cathode surface and the electrolyte, thus stabilizing the interface and cycle life. Furthermore, a full cell assembled with a graphite anode with an areal capacity of 3 mA h cm–2 displays a capacity retention of 90% over 300 cycles. Furthermore, the present work demonstrates an effective way to promote cation disordering and lower the surface reactivity of LNMO with the electrolyte, thereby enhancing the conductivity, stabilizing the cathode–electrolyte interphase, and making LNMO promising for practical applications.},
doi = {10.1021/acsaem.1c02903},
journal = {ACS Applied Energy Materials},
number = 11,
volume = 4,
place = {United States},
year = {Thu Nov 11 00:00:00 EST 2021},
month = {Thu Nov 11 00:00:00 EST 2021}
}
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https://doi.org/10.1021/acsaem.1c02903
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