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Title: Native Vacancy Enhanced Oxygen Redox Reversibility and Structural Robustness

Journal Article · · Advanced Energy Materials
 [1];  [2];  [3];  [4];  [5];  [6]; ORCiD logo [7];  [3];  [7];  [4];  [5];  [5];  [1];  [1]
  1. Chinese Academy of Sciences (CAS), Beijing (China); Univ. of Chinese Academy of Sciences, Beijing (China)
  2. Chinese Academy of Sciences (CAS), Beijing (China); Univ. of California San Diego, La Jolla, CA (United States)
  3. California State Univ. Northridge, Northridge, CA (United States)
  4. Chinese Academy of Sciences (CAS), Beijing (China)
  5. Argonne National Lab. (ANL), Lemont, IL (United States)
  6. Synchrotron Soleil, L'Orme des Merisiers St-Aubin, Gif-sur-Yvette Cedex (France)
  7. Brookhaven National Lab. (BNL), Upton, NY (United States)
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Cathode materials with high energy density, long cycle life, and low cost are of top priority for energy storage systems. The Li-rich transition metal (TM) oxides achieve high specific capacities by redox reactions of both the TM and oxygen ions. However, the poor reversible redox reaction of the anions results in severe fading of the cycling performance. Herein, the vacancy-containing Na-4/7[Mn-6/7(square(Mn))(1/7)]O-2 (square(Mn) for vacancies in the Mn - O slab) is presented as a novel cathode material for Na-ion batteries. The presence of native vacancies endows this material with attractive properties including high structural flexibility and stability upon Na-ion extraction and insertion and high reversibility of oxygen redox reaction. Synchrotron X-ray absorption near edge structure and X-ray photoelectron spectroscopy studies demonstrate that the charge compensation is dominated by the oxygen redox reaction and Mn3+/Mn4+ redox reaction separately. In situ synchrotron X-ray diffraction exhibits its zero-strain feature during the cycling. Density functional theory calculations further deepen the understanding of the charge compensation by oxygen and manganese redox reactions and the immobility of the Mn ions in the material. These findings provide new ideas on searching for and designing materials with high capacity and high structural stability for novel energy storage systems.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE) - Office of Vehicle Technologies (VTO); National Natural Science Foundation of China (NSFC)
Grant/Contract Number:
SC0012704; DE‐AC02‐06CH11357; DE‐SC0012704; AC02-06CH11357
OSTI ID:
1491135
Alternate ID(s):
OSTI ID: 1484544; OSTI ID: 1530186
Report Number(s):
BNL-210860-2019-JAAM
Journal Information:
Advanced Energy Materials, Vol. 9, Issue 4; ISSN 1614-6832
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 61 works
Citation information provided by
Web of Science

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Cited By (3)

Defect Engineering on Electrode Materials for Rechargeable Batteries journal November 2019
Interfacial Lattice‐Strain‐Driven Generation of Oxygen Vacancies in an Aerobic‐Annealed TiO 2 (B) Electrode journal November 2019
Ti-based electrode materials for electrochemical sodium ion storage and removal journal January 2019

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Related Subjects

25 ENERGY STORAGE
characterization techniques
ex situ
in situ
sodium-ion batteries
cathode materials
charge compensation
oxygen redox
sodium manganese oxide
zero-strain