Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Uncovering the predictive pathways of lithium and sodium interchange in layered oxides

Journal Article · · Nature Materials
 [1];  [2];  [1];  [3];  [3];  [1];  [1];  [1];  [1];  [4];  [5];  [6];  [1]
  1. Univ. of Chicago, IL (United States)
  2. National Univ. of Singapore (Singapore)
  3. Northwestern Univ., Evanston, IL (United States)
  4. Univ. of Illinois, Chicago, IL (United States)
  5. Argonne National Laboratory (ANL), Argonne, IL (United States)
  6. Univ. of Houston, TX (United States)
+ Show Author Affiliations

Ion exchange is a powerful method to access metastable materials with advanced functionalities for energy storage applications. However, high concentrations and unfavourably large excesses of lithium are always used for synthesizing lithium cathodes from parent sodium material, and the reaction pathways remain elusive. Here, using layered oxides as model materials, we demonstrate that vacancy level and its corresponding lithium preference are critical in determining the accessible and inaccessible ion exchange pathways. Taking advantage of the strong lithium preference at the right vacancy level, we establish predictive compositional and structural evolution at extremely dilute and low excess lithium based on the phase equilibrium between Li0.94CoO2 and Na0.48CoO2. Such phase separation behaviour is general in both surface reaction-limited and diffusion-limited exchange conditions and is accomplished with the charge redistribution on transition metals. Guided by this understanding, we demonstrate the synthesis of NayCoO2 from the parent LixCoO2 and the synthesis of Li0.94CoO2 from NayCoO2 at 1-1,000 Li/Na (molar ratio) with an electrochemical assisted ion exchange method by mitigating the kinetic barriers. Our study opens new opportunities for ion exchange in predictive synthesis and separation applications. Ion exchange is a powerful method to access metastable materials for energy storage, but identifying lithium and sodium interchange in layered oxides remains challenging. Using such model materials, vacancy level and corresponding lithium preference are shown to be crucial for ion exchange pathway accessibility.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC); USDOE Laboratory Directed Research and Development (LDRD) Program
Grant/Contract Number:
SC0022231; AC02-06CH11357
OSTI ID:
2570604
Journal Information:
Nature Materials, Journal Name: Nature Materials Journal Issue: 7 Vol. 23; ISSN 1476-4660; ISSN 1476-1122
Publisher:
Springer NatureCopyright Statement
Country of Publication:
United States
Language:
English

References (48)

Anisotropic Electrical Conductivity in LiCoO2 Single Crystal journal February 2002
Crystal Structure, Electric and Magnetic Properties of Layered Cobaltite β-NaxCoO2 journal June 2002
A new variety of LiCoO2 with an unusual oxygen packing obtained by exchange reaction journal January 1982
A new variety of LiMnO2 with a layered structure journal August 1996
Structural classification and properties of the layered oxides journal January 1980
On the metastable O2-type LiCoO2 journal December 2001
Studies of the layered manganese bronzes, Na2/3[Mn1−xMx]O2 with M=Co, Ni, Li, and Li2/3[Mn1−xMx]O2 prepared by ion-exchange journal November 1999
Python Materials Genomics (pymatgen): A robust, open-source python library for materials analysis journal February 2013
Determination of state of charge-dependent asymmetric Butler–Volmer kinetics for LixCoO2 electrode using GITT measurements journal December 2015
On the mechanism of the P2–Na0.70CoO2→O2–LiCoO2 exchange reaction—Part I: proposition of a model to describe the P2–O2 transition journal August 2004
On the mechanism of the P2–Na0.70CoO2→O2–LiCoO2 exchange reaction—Part II: an in situ X-ray diffraction study journal August 2004
Layer spacing gradient (NaLi)1−CoO2 for electrochemical Li extraction journal May 2021
Role of Crystal Symmetry in the Reversibility of Stacking-Sequence Changes in Layered Intercalation Electrodes journal November 2017
Sodium Doping to Enhance Electrochemical Performance of Overlithiated Oxide Cathode Materials for Li-Ion Batteries via Li/Na Ion-Exchange Method journal July 2018
Anisotropic Cation Exchange in PbSe/CdSe Core/Shell Nanocrystals of Different Geometry journal December 2011
Insights into Diffusion Mechanisms in P2 Layered Oxide Materials by First-Principles Calculations journal September 2014
Synthesis and Stoichiometry of Different Layered Sodium Cobalt Oxides journal September 2014
Electron Transfer Mechanisms upon Lithium Deintercalation from LiCoO 2 to CoO 2 Investigated by XPS journal January 2008
Layered T2-, O6-, O2-, and P2-Type A 2/3 [M‘ 2+ 1/3 M 4+ 2/3 ]O 2 Bronzes, A = Li, Na; M‘ = Ni, Mg; M = Mn, Ti journal August 2000
Ion-Exchange Mechanism of Layered Transition-Metal Oxides: Case Study of LiNi 0.5 Mn 0.5 O 2 journal July 2014
Ion Exchange Synthesis of III–V Nanocrystals journal November 2012
Cu Vacancies Boost Cation Exchange Reactions in Copper Selenide Nanocrystals journal July 2015
In Situ Tracking Kinetic Pathways of Li + /Na + Substitution during Ion-Exchange Synthesis of Li x Na 1.5– x VOPO 4 F 0.5 journal August 2017
Tailoring ZnSe–CdSe Colloidal Quantum Dots via Cation Exchange: From Core/Shell to Alloy Nanocrystals journal August 2013
Synthesis of layered LiMnO2 as an electrode for rechargeable lithium batteries journal June 1996
Ion exchange in atomically thin clays and micas journal August 2021
Alluaudite LiMnPO 4 : a new Mn-based positive electrode for Li rechargeable batteries journal January 2014
The insulator-metal transition upon lithium deintercalation from LiCoO2: electronic properties and 7Li NMR study journal January 1999
LiFePO4 with an alluaudite crystal structure for lithium ion batteries journal January 2013
Ion exchange selectivity in clay is controlled by nanoscale chemical–mechanical coupling journal October 2019
Ab initiomolecular dynamics for liquid metals journal January 1993
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study journal January 1998
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
Linear response approach to the calculation of the effective interaction parameters in the LDA + U method journal January 2005
Crystal structure and elementary properties of Na x Co O 2 ( x = 0.32 , 0.51, 0.6, 0.75, and 0.92) in the three-layer Na Co O 2 family journal May 2006
Generalized Gradient Approximation Made Simple journal October 1996
Na x CoO 2 phase stability and hierarchical orderings in the O3/P3 structure family journal January 2019
Cation Exchange Reactions in Ionic Nanocrystals journal November 2004
Electrodes with High Power and High Capacity for Rechargeable Lithium Batteries journal February 2006
Rational design of layered oxide materials for sodium-ion batteries journal November 2020
Covalent surface modifications and superconductivity of two-dimensional metal carbide MXenes journal July 2020
Determinants of crystal structure transformation of ionic nanocrystals in cation exchange reactions journal July 2021
The Effect of Co Substitution for Ni on the Structure and Electrochemical Behavior of T2 and O2 Structure Li[sub 2/3][Co[sub x]Ni[sub 1/3−x]Mn[sub 2/3]]O[sub 2] journal January 2001
Layered Li-Mn-Oxide with the O2 Structure: A Cathode Material for Li-Ion Cells Which Does Not Convert to Spinel journal January 1999
Layered LiCoO[sub 2] with a Different Oxygen Stacking (O2 Structure) as a Cathode Material for Rechargeable Lithium Batteries journal January 2000
O[sub 2]-Type Li[sub 2/3][Ni[sub 1/3]Mn[sub 2/3]]O[sub 2]: A New Layered Cathode Material for Rechargeable Lithium Batteries II. Structure, Composition, and Properties journal January 2000
T2 and O2 Li[sub 2/3][Co[sub x]Ni[sub 1/3−x/2]Mn[sub 2/3−x/2]]O[sub 2] Electrode Materials journal January 2002

Similar Records

Layer spacing gradient (NaLi)1–xCoO2 for electrochemical Li extraction
Journal Article · Sun Feb 28 23:00:00 EST 2021 · Matter (Online) · OSTI ID:1909331
The stabilization of layered manganese oxides for use in rechargeable lithium batteries
Conference · Fri Jun 30 20:00:00 EDT 2000 · OSTI ID:20086867
Structural and thermodynamic properties of cointercalated titanium disulfide
Journal Article · Mon Sep 01 00:00:00 EDT 1986 · J. Electrochem. Soc.; (United States) · OSTI ID:6954432

Related Subjects

25 ENERGY STORAGE
chemical engineering
electrochemistry
solid-state chemistry