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Title: Unraveling the Voltage-Fade Mechanism in High-Energy-Density Lithium-Ion Batteries: Origin of the Tetrahedral Cations for Spinel Conversion

Journal Article · · Chemistry of Materials
DOI:https://doi.org/10.1021/cm5031415· OSTI ID:1159409
 [1];  [1];  [2];  [1];  [1];  [3];  [3]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States). Bredesen Center for Interdisciplinary Research and Graduate Education
+ Show Author Affiliations

Discovery of high-voltage layered lithium-and manganese-rich (LMR) composite oxide electrode has dramatically enhanced the energy density of current Li-ion energy storage systems. However, practical usage of these materials is currently not viable because of their inability to maintain a consistent voltage profile (voltage fading) during subsequent charge-discharge cycles. This report rationalizes the cause of this voltage fade by providing the evidence of layer to spinel-like (LSL) structural evolution pathways in the host Li1.2Mn0.55Ni0.15Co0.1O2 LMR composite oxide. By employing neutron powder diffraction, and temperature dependent magnetic susceptibility, we show that LSL structural rearrangement in LMR oxide occurs through a tetrahedral cation intermediate via: i) diffusion of lithium atoms from octahedral to tetrahedral sites of the lithium layer [(LiLioct →LiLitet] which is followed by the dispersal of the lithium ions from the adjacent octahedral site of the metal layer to the tetrahedral sites of lithium layer [LiTM oct → LiLitet]; and ii) migration of Mn from the octahedral sites of the transition metal layer to the permanent octahedral site of lithium layer via tetrahedral site of lithium layer [MnTMoct MnLitet MnLioct)]. The findings opens the door to the potential routes to mitigate this atomic restructuring in the high-voltage LMR composite oxide cathodes by manipulating the composition/structure for practical use in high-energy-density lithium-ion batteries.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1159409
Journal Information:
Chemistry of Materials, Vol. 26, Issue 21; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 207 works
Citation information provided by
Web of Science

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Cited By (35)

Metal–oxygen decoordination stabilizes anion redox in Li-rich oxides journal February 2019
Voltage Decay in Layered Li-Rich Mn-Based Cathode Materials journal August 2019
On the dynamics of transition metal migration and its impact on the performance of layered oxides for sodium-ion batteries: NaFeO 2 as a case study journal January 2018
Unveiling the benefits of potassium doping on the structural integrity of Li–Mn-rich layered oxides during prolonged cycling by dual-mode EPR spectroscopy journal January 2019
Voltage fade mitigation in the cationic dominant lithium-rich NCM cathode journal October 2019
Cation-disordered rocksalt transition metal oxides and oxyfluorides for high energy lithium-ion cathodes journal January 2020
Na-ion battery cathode materials prepared by electrochemical ion exchange from alumina-coated Li 1+x Mn 0.54 Co 0.13 Ni 0.1+y O 2 journal January 2018
Review on anionic redox for high-capacity lithium- and sodium-ion batteries journal April 2017
Modification of Ni-Rich FCG NMC and NCA Cathodes by Atomic Layer Deposition: Preventing Surface Phase Transitions for High-Voltage Lithium-Ion Batteries journal May 2016
Insight of a Phase Compatible Surface Coating for Long‐Durable Li‐Rich Layered Oxide Cathode journal July 2019
A stable layered P3/P2 and spinel intergrowth nanocomposite as a long-life and high-rate cathode for sodium-ion batteries journal January 2018
Injection of oxygen vacancies in the bulk lattice of layered cathodes journal April 2019
Review—Recent Advances and Remaining Challenges for Lithium Ion Battery Cathodes: II. Lithium-Rich, xLi journal January 2017
Sodium-Alginate-Based Binders for Lithium-Rich Cathode Materials in Lithium-Ion Batteries to Suppress Voltage and Capacity Fading journal March 2018
Review—Lithium-Excess Layered Cathodes for Lithium Rechargeable Batteries journal January 2015
Slightly Fluorination of Al 2 O 3 ALD Coating on Li 1.2 Mn 0.54 Co 0.13 Ni 0.13 O 2 Electrodes: Interface Reaction to Create Stable Solid Permeable Interphase Layer journal January 2019
High-Performance Lithium-Rich Layered Oxide Material: Effects of Preparation Methods on Microstructure and Electrochemical Properties journal January 2020
Toward Low-Cost, High-Energy Density, and High-Power Density Lithium-Ion Batteries journal June 2017
Ecofriendly Chemical Activation of Overlithiated Layered Oxides by DNA‐Wrapped Carbon Nanotubes journal January 2020
Atomic-Scale Structure Evolution in a Quasi-Equilibrated Electrochemical Process of Electrode Materials for Rechargeable Batteries journal February 2015
High-voltage positive electrode materials for lithium-ion batteries journal January 2017
Nickel-Rich and Lithium-Rich Layered Oxide Cathodes: Progress and Perspectives journal October 2015
Li 1.2 Mn 0.55 Ni 0.15 Co 0.1 O 2 (LMR-NMC)-Carbon Coated-LiMnPO 4 Blended Electrodes for High Performance Lithium Ion Batteries journal January 2018
Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes journal January 2020
Effect of Potassium Doping on the Electrochemical Properties of 0.5Li 2 MnO 3 -0.5LiMn 0.375 Ni 0.375 Co 0.25 O 2 Cathode journal January 2018
Unraveling the Voltage Decay Phenomenon in Li‐Rich Layered Oxide Cathode of No Oxygen Activity journal October 2019
A multiscale investigation elucidating the structural complexities and electrochemical properties of layered–layered composite cathode materials synthesized at low temperatures journal January 2020
Investigation of Interfacial Changes on Grain Boundaries of Li(Ni 0.5 Co 0.2 Mn 0.3 )O 2 in the Initial Overcharge Process journal February 2019
Lithium/Oxygen Incorporation and Microstructural Evolution during Synthesis of Li-Rich Layered Li[Li 0.2 Ni 0.2 Mn 0.6 ]O 2 Oxides journal February 2019
Enhanced rate performance and cycle stability of LiNi0.8Co0.15Al0.05O2 via Rb doping journal October 2018
Suppressing the voltage-fading of layered lithium-rich cathode materials via an aqueous binder for Li-ion batteries journal January 2016
Enhanced cycling stability of boron-doped lithium-rich layered oxide cathode materials by suppressing transition metal migration journal January 2019
Editors' Choice—State of Charge Dependent Resistance Build-Up in Li- and Mn-Rich Layered Oxides during Lithium Extraction and Insertion journal January 2019
Understanding the structure and structural degradation mechanisms in high-voltage, lithium-manganese–rich lithium-ion battery cathode oxides: A review of materials diagnostics journal January 2015
Structural evolution at the oxidative and reductive limits in the first electrochemical cycle of Li1.2Ni0.13Mn0.54Co0.13O2 journal March 2020

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Related Subjects

25 ENERGY STORAGE
Neutron diffraction
lithium rich
magnetic susceptibility
phase transformation
voltage fade
lithium ion batteries