skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Abstract

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 themore » 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:
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)
OSTI Identifier:
1461415
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: 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)
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

Citation Formats

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., 2017. 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. https://doi.org/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. https://doi.org/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},
url = {https://www.osti.gov/biblio/1461415}, journal = {ACS Applied Materials and Interfaces},
issn = {1944-8244},
number = 1,
volume = 10,
place = {United States},
year = {Fri Nov 03 00:00:00 EDT 2017},
month = {Fri Nov 03 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 22 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Is lithium the new gold?
journal, June 2010


Structural classification and properties of the layered oxides
journal, January 1980


Electrochemical intercalation of sodium in NaxCoO2 bronzes
journal, August 1981


Etude par desintercalation electrochimique des systemes NaxCrO2 et NaxNiO2
journal, August 1982


Electronic and electrochemical properties of NaxCoO2−y cathode
journal, December 1983


Electrochemical intercalation and deintercalation of NaxMnO2 bronzes
journal, May 1985


Research Development on Sodium-Ion Batteries
journal, October 2014


In Situ X-Ray Diffraction Study of P2-Na[sub 2/3][Ni[sub 1/3]Mn[sub 2/3]]O[sub 2]
journal, January 2001


P2-type Nax[Fe1/2Mn1/2]O2 made from earth-abundant elements for rechargeable Na batteries
journal, April 2012


P2-Na x Mn 1/2 Fe 1/2 O 2 Phase Used as Positive Electrode in Na Batteries: Structural Changes Induced by the Electrochemical (De)intercalation Process
journal, September 2014


Rechargeable Electrodes from Sodium Cobalt Bronzes
journal, January 1988


High performance Na x CoO 2 as a cathode material for rechargeable sodium batteries
journal, January 2015


Electrochemical investigation of the P2–NaxCoO2 phase diagram
journal, December 2010


Electronic origin of the step-like character of the discharge curve for Na x CoO 2-y cathode
journal, December 2014


Electrode Properties of P2–Na 2/3 Mn y Co 1– y O 2 as Cathode Materials for Sodium-Ion Batteries
journal, July 2013


Ca-doped Na x CoO 2 for improved cyclability in sodium ion batteries
journal, March 2015


Suppressing the P2-O2 Phase Transition of Na 0.67 Mn 0.67 Ni 0.33 O 2 by Magnesium Substitution for Improved Sodium-Ion Batteries
journal, May 2016


Novel P2-type Na 2/3 Ni 1/6 Mg 1/6 Ti 2/3 O 2 as an anode material for sodium-ion batteries
journal, January 2017


Toward Na-ion Batteries—Synthesis and Characterization of a Novel High Capacity Na Ion Intercalation Material
journal, January 2013


New P2 - Na 0.70 Mn 0.60 Ni 0.30 Co 0.10 O 2 Layered Oxide as Electrode Material for Na-Ion Batteries
journal, January 2014


High Capacity Positive Electrode Material for Room Temperature Na Ion Battery: Na x Mn 2/3 Co 1/6 Ni 1/6 O 2
journal, January 2015


Synthesis and characterization of a new layered cathode material for sodium ion batteries
journal, November 2014


P-type Na x Ni 0.22 Co 0.11 Mn 0.66 O 2 materials: linking synthesis with structure and electrochemical performance
journal, January 2014


X-ray Absorption Spectroscopic Study of Chemically and Electrochemically Li Ion Extracted Li y Co 0.85 Al 0.15 O 2 Compounds
journal, August 1999


In Situ X-ray Absorption Spectroscopic Study on LiNi 0.5 Mn 0.5 O 2 Cathode Material during Electrochemical Cycling
journal, August 2003


Passivation Layer and Cathodic Redox Reactions in Sodium-Ion Batteries Probed by HAXPES
journal, December 2015


Local structure of LiNi0.5Mn0.5O2 cathode material probed by in situ x-ray absorption spectroscopy
journal, March 2006


Enhanced Sodium Ion Storage Behavior of P2-Type Na 2/3 Fe 1/2 Mn 1/2 O 2 Synthesized via a Chelating Agent Assisted Route
journal, January 2016


Nuclear quadrupole resonance and x-ray investigation of the structure of Na 2 / 3 CoO 2
journal, December 2009


Low temperature phase transitions and crystal structure of Na 0.5 CoO 2
journal, August 2004


An investigation of the sodium patterning in NaxCoO2 (0.5⩽x⩽1) by density functional theory methods
journal, March 2008


Theory of sodium ordering in Na x Co O 2
journal, April 2005


Patterning of sodium ions and the control of electrons in sodium cobaltate
journal, February 2007


Ab initio study of sodium ordering in Na 0.75 Co O 2 and its relation to Co 3 + Co 4 + charge ordering
journal, November 2005


An advanced cathode for Na-ion batteries with high rate and excellent structural stability
journal, January 2013


Structure of the high voltage phase of layered P2-Na 2/3−z [Mn 1/2 Fe 1/2 ]O 2 and the positive effect of Ni substitution on its stability
journal, January 2015


Charge compensation and oxidation in NaxCoO2−δ and LixCoO2−δ studied by XANES
journal, May 2007


Detailed Studies of a High-Capacity Electrode Material for Rechargeable Batteries, Li 2 MnO 3 −LiCo 1/3 Ni 1/3 Mn 1/3 O 2
journal, March 2011


Exploring Oxygen Activity in the High Energy P2-Type Na 0.78 Ni 0.23 Mn 0.69 O 2 Cathode Material for Na-Ion Batteries
journal, March 2017


Works referencing / citing this record:

Ni-based cathode materials for Na-ion batteries
journal, June 2019


A study of the electrochemical kinetics of sodium intercalation in P2/O1/O3-NaNi1/3Mn1/3Co1/3O2
journal, December 2019


Recent Progress of Layered Transition Metal Oxide Cathodes for Sodium‐Ion Batteries
journal, February 2019


A First-Principles and Experimental Investigation of Nickel Solubility into the P2 Na x CoO 2 Sodium-Ion Cathode
journal, August 2018


Nanoparticles Assembled Microspheres as a High-Rate Cathode Material for Sodium Ion Batteries
journal, January 2019