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Title: On the P2-Na xCo 1–y (Mn 2/3Ni 1/3) yO 2 Cathode Materials for Sodium-Ion Batteries: Synthesis, Electrochemical Performance, and Redox Processes Occurring during the Electrochemical Cycling

P2-type NaMO 2 sodiated layered oxides with mixed transition metals are receiving considerable attention for use as cathodes in sodium-ion batteries. A study on solid solution (1 – y)P2-Na xCoO 2–( y)P2-Na xMn 2/3Ni 1/3O 2 ( y = 0, 1/3, 1/2, 2/3, 1) reveals that changing the composition of the transition metals affects the resulting structure and the stability of pure P2 phases at various temperatures of calcination. For 0 ≤ y ≤ 1.0, the P2-Na xCo (1–y)Mn 2y/3Ni y/3O 2 solid-solution compounds deliver good electrochemical performance when cycled between 2.0 and 4.2 V versus Na +/Na with improved capacity stability in long-term cycling, especially for electrode materials with lower Co content ( y = 1/2 and 2/3), despite lower discharge capacities being observed. The (1/2)P2-Na xCoO 2–(1/2)P2-Na xMn 2/3Ni 1/3O 2 composition delivers a discharge capacity of 101.04 mAh g –1 with a capacity loss of only 3% after 100 cycles and a Coulombic efficiency exceeding 99.2%. Cycling this material to a higher cutoff voltage of 4.5 V versus Na +/Na increases the specific discharge capacity to ≈140 mAh g –1 due to the appearance of a well-defined high-voltage plateau, but after only 20 cycles, capacity retention declinesmore » to 88% and Coulombic efficiency drops to around 97%. In situ X-ray absorption near-edge structure measurements conducted on composition Na xCo 1/2Mn 1/3Ni 1/6O 2 ( y = 1/2) in the two potential windows studied help elucidate the operating potential of each transition metal redox couple. As a result, it also reveals that at the high-voltage plateau, all of the transition metals are stable, raising the suspicion of possible contribution of oxygen ions in the high-voltage plateau.« less
Authors:
 [1] ;  [2] ;  [3] ;  [4] ;  [2] ;  [5] ; ORCiD logo [2] ;  [2] ; ORCiD logo [3] ; ORCiD logo [3] ; ORCiD logo [6]
  1. Univ. Cadi Ayyad (UCA), Marrakech (Morocco); Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Argonne National Lab. (ANL), Lemont, IL (United States)
  3. Uppsala Univ., Uppsala (Sweden)
  4. Univ. Cadi Ayyad (UCA), Marrakech (Morocco)
  5. Mohammed VI Polytechnic Univ. (UM6P), Ben Guerir (Morocco)
  6. Univ. Cadi Ayyad (UCA), Marrakech (Morocco); Mohammed VI Polytechnic Univ. (UM6P), Ben Guerir (Morocco)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; energy storage; high-voltage plateau; in situ XANES measurements; Na-ion batteries; P2-type materials
OSTI Identifier:
1461415

Doubaji, Siham, Ma, Lu, Asfaw, Habtom Desta, Izanzar, Ilyasse, Xu, Rui, Alami, Jones, Lu, Jun, Wu, Tianpin, Amine, Khalil, Edström, Kristina, and Saadoune, Ismael. On the P2-NaxCo1–y (Mn2/3Ni1/3)yO2 Cathode Materials for Sodium-Ion Batteries: Synthesis, Electrochemical Performance, and Redox Processes Occurring during the Electrochemical Cycling. United States: N. p., Web. doi:10.1021/acsami.7b13472.
Doubaji, Siham, Ma, Lu, Asfaw, Habtom Desta, Izanzar, Ilyasse, Xu, Rui, Alami, Jones, Lu, Jun, Wu, Tianpin, Amine, Khalil, Edström, Kristina, & Saadoune, Ismael. On the P2-NaxCo1–y (Mn2/3Ni1/3)yO2 Cathode Materials for Sodium-Ion Batteries: Synthesis, Electrochemical Performance, and Redox Processes Occurring during the Electrochemical Cycling. United States. doi:10.1021/acsami.7b13472.
Doubaji, Siham, Ma, Lu, Asfaw, Habtom Desta, Izanzar, Ilyasse, Xu, Rui, Alami, Jones, Lu, Jun, Wu, Tianpin, Amine, Khalil, Edström, Kristina, and Saadoune, Ismael. 2017. "On the P2-NaxCo1–y (Mn2/3Ni1/3)yO2 Cathode Materials for Sodium-Ion Batteries: Synthesis, Electrochemical Performance, and Redox Processes Occurring during the Electrochemical Cycling". United States. doi:10.1021/acsami.7b13472. https://www.osti.gov/servlets/purl/1461415.
@article{osti_1461415,
title = {On the P2-NaxCo1–y (Mn2/3Ni1/3)yO2 Cathode Materials for Sodium-Ion Batteries: Synthesis, Electrochemical Performance, and Redox Processes Occurring during the Electrochemical Cycling},
author = {Doubaji, Siham and Ma, Lu and Asfaw, Habtom Desta and Izanzar, Ilyasse and Xu, Rui and Alami, Jones and Lu, Jun and Wu, Tianpin and Amine, Khalil and Edström, Kristina and Saadoune, Ismael},
abstractNote = {P2-type NaMO2 sodiated layered oxides with mixed transition metals are receiving considerable attention for use as cathodes in sodium-ion batteries. A study on solid solution (1 – y)P2-NaxCoO2–(y)P2-NaxMn2/3Ni1/3O2 (y = 0, 1/3, 1/2, 2/3, 1) reveals that changing the composition of the transition metals affects the resulting structure and the stability of pure P2 phases at various temperatures of calcination. For 0 ≤ y ≤ 1.0, the P2-NaxCo(1–y)Mn2y/3Niy/3O2 solid-solution compounds deliver good electrochemical performance when cycled between 2.0 and 4.2 V versus Na+/Na with improved capacity stability in long-term cycling, especially for electrode materials with lower Co content (y = 1/2 and 2/3), despite lower discharge capacities being observed. The (1/2)P2-NaxCoO2–(1/2)P2-NaxMn2/3Ni1/3O2 composition delivers a discharge capacity of 101.04 mAh g–1 with a capacity loss of only 3% after 100 cycles and a Coulombic efficiency exceeding 99.2%. Cycling this material to a higher cutoff voltage of 4.5 V versus Na+/Na increases the specific discharge capacity to ≈140 mAh g–1 due to the appearance of a well-defined high-voltage plateau, but after only 20 cycles, capacity retention declines to 88% and Coulombic efficiency drops to around 97%. In situ X-ray absorption near-edge structure measurements conducted on composition NaxCo1/2Mn1/3Ni1/6O2 (y = 1/2) in the two potential windows studied help elucidate the operating potential of each transition metal redox couple. As a result, it also reveals that at the high-voltage plateau, all of the transition metals are stable, raising the suspicion of possible contribution of oxygen ions in the high-voltage plateau.},
doi = {10.1021/acsami.7b13472},
journal = {ACS Applied Materials and Interfaces},
number = 1,
volume = 10,
place = {United States},
year = {2017},
month = {11}
}