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Title: Improved Cycling Performance of Li-Excess Cation-Disordered Cathode Materials upon Fluorine Substitution

Journal Article · · Advanced Energy Materials
 [1];  [1];  [2];  [3];  [4];  [5];  [3];  [4];  [1];  [6];  [3]; ORCiD logo [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  4. Univ. of California, Berkeley, CA (United States)
  5. Argonne National Lab. (ANL), Argonne, IL (United States)
  6. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
+ Show Author Affiliations

We report the recent discovery of Li-excess cation-disordered rock salt cathodes has greatly enlarged the design space of Li-ion cathode materials. Evidence of facile lattice fluorine substitution for oxygen has further provided an important strategy to enhance the cycling performance of this class of materials. Here, a group of Mn3+–Nb5+-based cation-disordered oxyfluorides, Li1.2Mn3+0.6+0.5xNb5+0.2-0.5xO2-xFx (x = 0, 0.05, 0.1, 0.15, 0.2) is investigated and it is found that fluorination improves capacity retention in a very significant way. Combining spectroscopic methods and ab initio calculations, it is demonstrated that the increased transition-metal redox (Mn3+/Mn4+) capacity that can be accommodated upon fluorination reduces reliance on oxygen redox and leads to less oxygen loss, as evidenced by differential electrochemical mass spectroscopy measurements. Furthermore, it is found that fluorine substitution also decreases the Mn3+-induced Jahn–Teller distortion, leading to an orbital rearrangement that further increases the contribution of Mn-redox capacity to the overall capacity.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Robert Bosch GmbH; Umicore
Grant/Contract Number:
AC02-06CH11357; AC02-05CH11231
OSTI ID:
1493873
Journal Information:
Advanced Energy Materials, Journal Name: Advanced Energy Materials Journal Issue: 2 Vol. 9; ISSN 1614-6832
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (8)

Effect of Fluorination on Lithium Transport and Short‐Range Order in Disordered‐Rocksalt‐Type Lithium‐Ion Battery Cathodes journal March 2020
A High‐Energy NASICON‐Type Cathode Material for Na‐Ion Batteries journal March 2020
Gassing Behavior of High‐Entropy Oxide Anode and Oxyfluoride Cathode Probed Using Differential Electrochemical Mass Spectrometry journal April 2020
Multi-anionic and -cationic compounds: new high entropy materials for advanced Li-ion batteries journal January 2019
Cation-disordered rocksalt transition metal oxides and oxyfluorides for high energy lithium-ion cathodes journal January 2020
Multi-anionic and -cationic compounds: new high entropy materials for advanced Li-ion batteries other January 2019
Multi-anionic and -cationic compounds: New high entropy materials for advanced Li-ion batteries other January 2019
Gassing Behavior of High‐Entropy Oxide Anode and Oxyfluoride Cathode Probed Using Differential Electrochemical Mass Spectrometry text January 2020

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Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
DFT
Jahn–Teller distortion
Li‐excess cation‐disordered cathodes
cyclability
fluorination