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Enabling the high capacity of lithium-rich anti-fluorite lithium iron oxide by simultaneous anionic and cationic redox

Journal Article · · Nature Energy
 [1];  [2];  [1];  [3];  [1];  [4];  [1];  [3];  [3];  [4];  [3];  [1];  [1];  [4];  [2];  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  2. Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering
  3. Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Div.
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
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Anionic redox reactions in cathodes of lithium-ion batteries are allowing opportunities to double or even triple the energy density. However, it is still challenging to develop a cathode, especially with Earth-abundant elements, that enables anionic redox activity for real-world applications, primarily due to limited strategies to intercept the oxygenates from further irreversible oxidation to O2 gas. Here we report simultaneous iron and oxygen redox activity in a Li-rich anti-fluorite Li5FeO4 electrode. During the removal of the first two Li ions, the oxidation potential of O2- is lowered to approximately 3.5 V versus Li+/Li0, at which potential the cationic oxidation occurs concurrently. These anionic and cationic redox reactions show high reversibility without any obvious O2 gas release. Moreover, this study provides an insightful guide to designing high-capacity cathodes with reversible oxygen redox activity by simply introducing oxygen ions that are exclusively coordinated by Li+.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
DOE Contract Number:
AC02-06CH11357; AC02-05CH11231
OSTI ID:
1490269
Journal Information:
Nature Energy, Vol. 2, Issue 12; ISSN 2058-7546
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English

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Interplay of cation and anion redox in Li 4 Mn 2 O 5 cathode material and prediction of improved Li 4 (Mn,M) 2 O 5 electrodes for Li-ion batteries journal May 2018
The Absence and Importance of Operando Techniques for Metal‐Free Catalysts journal November 2018
The Synergic Effects of Zr Doping and Li 2 TiO 3 Coating on the Crystal Structure and Electrochemical Performances of Li-Rich Li 1.2 Ni 0.2 Mn 0.6 O 2 journal January 2019
Combined Theoretical and Experimental Studies of Sodium Battery Materials journal November 2018
Manganese‐Based Na‐Rich Materials Boost Anionic Redox in High‐Performance Layered Cathodes for Sodium‐Ion Batteries journal May 2019
Dynamic imaging of crystalline defects in lithium-manganese oxide electrodes during electrochemical activation to high voltage journal April 2019
Fundamental Insights from a Single‐Crystal Sodium Iridate Battery journal March 2020
Self-sacrificial organic lithium salt enhanced initial Coulombic efficiency for safer and greener lithium-ion batteries journal January 2019
Aqueous Li-ion battery enabled by halogen conversion–intercalation chemistry in graphite journal May 2019
Tuning Anionic Redox Activity and Reversibility for a High‐Capacity Li‐Rich Mn‐Based Oxide Cathode via an Integrated Strategy journal March 2019
Native Vacancy Enhanced Oxygen Redox Reversibility and Structural Robustness journal December 2018
Metal–oxygen decoordination stabilizes anion redox in Li-rich oxides journal February 2019
Discovery of Calcium-Metal Alloy Anodes for Reversible Ca-Ion Batteries journal January 2019
An oxalate cathode for lithium ion batteries with combined cationic and polyanionic redox journal August 2019
Suppression of Voltage Decay through Manganese Deactivation and Nickel Redox Buffering in High-Energy Layered Lithium-Rich Electrodes journal May 2018
The quest for manganese-rich electrodes for lithium batteries: strategic design and electrochemical behavior journal January 2018
Short-range ordering in a battery electrode, the ‘cation-disordered’ rocksalt Li 1.25 Nb 0.25 Mn 0.5 O 2 journal January 2019
Correlation between manganese dissolution and dynamic phase stability in spinel-based lithium-ion battery journal October 2019
A high-pressure induced stable phase of Li 2 MnSiO 4 as an effective poly-anion cathode material from simulations journal January 2019
Simultaneously Dual Modification of Ni‐Rich Layered Oxide Cathode for High‐Energy Lithium‐Ion Batteries journal February 2019

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