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Origins of Irreversibility in Layered NaNixFeyMnzO2 Cathode Materials for Sodium Ion Batteries

Journal Article · · ACS Applied Materials and Interfaces
 [1];  [2];  [2];  [3];  [2];  [2];  [3];  [2];  [3];  [4]
  1. Boise State Univ., ID (United States); Boise State University
  2. Boise State Univ., ID (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Boise State Univ., ID (United States); Center for Advanced Energy Studies (CAES), Idaho Falls, ID (United States)
+ Show Author Affiliations
Layered NaNixFeyMnzO2 cathode (NFM) is of great interest in sodium ion batteries due to its high theoretical capacity and utilization of abundant, low-cost, environmentally-friendly raw materials. Nevertheless, there remains insufficient understanding on the concurrent local environment evolution in each transition metal (TM) that largely influences the reversibility of the cathode materials upon cycling. In this work, we investigate the reversibility of TM ions in layered NFMs with varying Fe contents and potential windows. Utilizing ex situ synchrotron X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) of pre-cycled samples the valence and bonding evolution of the TMs are elucidated. It is found that Mn is electrochemically inactive as indicated by the insignificant change of Mn valence and Mn-O bonding distance. Fe is electrochemically inactive after the first five cycles. The Ni redox couple contributes most of the charge compensation for NFMs. Ni redox is quite reversible in the cathodes with less Fe contents. Furthermore, the Ni redox couple shows significant irreversibility with high Fe content of 0.8. The electrochemical reversibility of the NFM cathode becomes increasingly enhanced with the decrease of either Fe content or with lower upper charge cutoff potential.
Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); Boise State Univ., ID (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-06CH11357; SC0019121
OSTI ID:
1706706
Alternate ID(s):
OSTI ID: 1776848
Journal Information:
ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 46 Vol. 12; ISSN 1944-8244
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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25 ENERGY STORAGE
36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
X-ray absorption spectroscopy
layered transition metal oxide cathode
layered transition-metal oxide cathode
local environment evolution
reversibility
sodium ion battery
x-ray absorption spectroscopy