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Title: The Mechanism of Fluorine Doping for the Enhanced Lithium Storage Behavior in Cation-Disordered Cathode Oxide

Journal Article · · Advanced Energy Materials
 [1];  [1];  [2];  [2];  [2];  [3];  [4]; ORCiD logo [5];  [5];  [2]; ORCiD logo [1];  [1];  [2];  [2]
  1. Chinese Academy of Sciences (CAS), Beijing (China); University of Chinese Academy of Sciences, Beijing (China)
  2. Chinese Academy of Sciences (CAS), Beijing (China)
  3. Chinese Academy of Sciences (CAS), Beijing (China); Central South University, Changsha (China); BASF Shanshan Battery Materials Co., Ltd. (China)
  4. University of Chinese Academy of Sciences, Beijing (China); Chinese Academy of Sciences (CAS), Beijing (China); Songshan Lake Materials Laboratory, Guangdong (China)
  5. Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
+ Show Author Affiliations

Li-rich cation-disordered rock-salt (DRX) materials have emerged as promising candidates for high-capacity oxide cathodes. Their fluorinated variants have shown improved cycling stability with effectively suppressed oxygen loss. However, a comprehensive understanding of how fluorination impacts the multiscale structure and lithium transportation in DRX remains elusive in experiments. In this study, the neutron total scattering technique in conjunction with the advanced reverse Monte Carlo (RMC) fitting method is employed to characterize the intricate structure of Li1.16Ti0.37Ni0.37Nb0.1O2 (LTNNO) and the fluorinated Li1.2Ti0.35Ni0.35Nb0.1O1.8F0.2 (LTNNOF). Through rigorous statistical analysis, the multiscale structural evolution upon fluorination is quantified from atomic (≤5 Å) to long-range scale (≈100 Å). The local Li-rich environments around F induce a modest 2.4% increment in the number of fast Li 0TM (transition metal) channels. Crucially, at a broader scale, the proportion of 0TM channels participating in percolation increases significantly from 2.9% in LTNNO to 8.7% in LTNNOF. Fluorination improves the capacity release mainly through merging isolated fast Li channels into the percolation network. This work experimentally unravels the multiscale mechanism of fluorination-induced performance improvement in DRX materials and highlights the necessity of adopting an advanced RMC fitting method to obtain a full view of the complex structural features in developing high-capacity DRX cathodes.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
2251579
Journal Information:
Advanced Energy Materials, Vol. 13, Issue 47; ISSN 1614-6832
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

References (52)

Lithium diffusion mechanisms in layered intercalation compounds journal July 2001
Generalized Gradient Approximation Made Simple journal October 1996
Mantid—Data analysis and visualization package for neutron scattering and μ SR experiments
  • Arnold, O.; Bilheux, J. C.; Borreguero, J. M.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 764 https://doi.org/10.1016/j.nima.2014.07.029
journal November 2014
Reversible Mn2+/Mn4+ double redox in lithium-excess cathode materials journal April 2018
Li + intercalation in isostructural Li 2 VO 3 and Li 2 VO 2 F with O 2− and mixed O 2− /F − anions journal January 2015
Anionic redox reactions and structural degradation in a cation-disordered rock-salt Li1.2Ti0.4Mn0.4O2 cathode material revealed by solid-state NMR and EPR journal January 2020
Reversible Three-Electron Redox Reaction of Mo 3+ /Mo 6+ for Rechargeable Lithium Batteries journal March 2017
Inelasticity corrections for time-of-flight and fixed wavelength neutron diffraction experiments journal August 2009
The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials journal May 2016
Structural and mechanistic revelations on high capacity cation-disordered Li-rich oxides for rechargeable Li-ion batteries journal January 2019
Another Strategy, Detouring Potential Decay by Fast Completion of Cation Mixing journal February 2018
Unlocking the Potential of Cation-Disordered Oxides for Rechargeable Lithium Batteries journal January 2014
Reverse Monte Carlo modelling of the structure of disordered materials with RMC++ : a new implementation of the algorithm in C++ journal January 2005
Modeling Short-Range Order in Disordered Rocksalt Cathodes by Pair Distribution Function Analysis journal June 2023
Effect of fluorination and Li-excess on the Li migration barrier in Mn-based cathode materials journal January 2020
Design principles for high transition metal capacity in disordered rocksalt Li-ion cathodes journal January 2018
Understanding Performance Degradation in Cation‐Disordered Rock‐Salt Oxide Cathodes journal July 2019
Toward Better Stability and Reversibility of the Mn4+/Mn2+ Double Redox Activity in Disordered Rocksalt Oxyfluoride Cathode Materials journal October 2021
Disordered Lithium-Rich Oxyfluoride as a Stable Host for Enhanced Li + Intercalation Storage journal February 2015
Role of Redox‐Inactive Transition‐Metals in the Behavior of Cation‐Disordered Rocksalt Cathodes journal May 2020
Heavy Fluorination via Ion Exchange Achieves High‐Performance Li–Mn–O–F Layered Cathode for Li‐Ion Batteries journal December 2021
Hidden structural and chemical order controls lithium transport in cation-disordered oxides for rechargeable batteries journal February 2019
Building Practical High‐Voltage Cathode Materials for Lithium‐Ion Batteries journal August 2022
An Overview of Cation-Disordered Lithium-Excess Rocksalt Cathodes journal March 2021
Treatment of hydrogen background in bulk and nanocrystalline neutron total scattering experiments journal May 2011
Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials journal October 2017
Short-Range Order and Unusual Modes of Nickel Redox in a Fluorine-Substituted Disordered Rocksalt Oxide Lithium-Ion Cathode journal September 2018
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
Lithium manganese oxyfluoride as a new cathode material exhibiting oxygen redox journal January 2018
Unravelling Solid-State Redox Chemistry in Li 1.3 Nb 0.3 Mn 0.4 O 2 Single-Crystal Cathode Material journal February 2018
Unraveling the Nature and Role of Layered Cation Ordering in Cation-Disordered Rock-Salt Cathodes journal October 2022
Effect of Fluorination on Lithium Transport and Short‐Range Order in Disordered‐Rocksalt‐Type Lithium‐Ion Battery Cathodes journal March 2020
The Nanoscale Ordered MAterials Diffractometer NOMAD at the Spallation Neutron Source SNS
  • Neuefeind, Jörg; Feygenson, Mikhail; Carruth, John
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 287 https://doi.org/10.1016/j.nimb.2012.05.037
journal September 2012
Fluorination of Lithium-Excess Transition Metal Oxide Cathode Materials journal October 2017
Improved Cycling Performance of Li-Excess Cation-Disordered Cathode Materials upon Fluorine Substitution journal November 2018
Design Principles for High-Capacity Mn-Based Cation-Disordered Rocksalt Cathodes journal January 2020
Understanding the Effect of Local Short-Range Ordering on Lithium Diffusion in Li1.3Nb0.3Mn0.4O2 Single-Crystal Cathode journal September 2018
Anion Reactivity in Cation‐Disordered Rocksalt Cathode Materials: The Influence of Fluorine Substitution journal August 2020
Anionic redox induced anomalous structural transition in Ni-rich cathodes journal January 2021
Charge Compensation Mechanism of Lithium-Excess Metal Oxides with Different Covalent and Ionic Characters Revealed by Operando Soft and Hard X-ray Absorption Spectroscopy journal November 2019
RMCProfile: reverse Monte Carlo for polycrystalline materials journal July 2007
Advances in the Cathode Materials for Lithium Rechargeable Batteries journal February 2020
Correlating ligand-to-metal charge transfer with voltage hysteresis in a Li-rich rock-salt compound exhibiting anionic redox journal September 2021
Ultrahigh power and energy density in partially ordered lithium-ion cathode materials journal March 2020
Trace doping of multiple elements enables stable battery cycling of LiCoO2 at 4.6 V journal June 2019
Exceptional Cycling Performance Enabled by Local Structural Rearrangements in Disordered Rocksalt Cathodes journal May 2022
Structural and Electrochemical Insights from the Fluorination of Disordered Mn-Based Rock Salt Cathode Materials journal February 2022
Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries journal December 2016
Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points journal December 2000
Fluorination effect for stabilizing cationic and anionic redox activities in cation-disordered cathode materials journal November 2020
Expandable Li Percolation Network: The Effects of Site Distortion in Cation-Disordered Rock-Salt Cathode Material journal May 2023
Cation-disordered rocksalt transition metal oxides and oxyfluorides for high energy lithium-ion cathodes journal January 2020

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25 ENERGY STORAGE
cathodes
cation-disordered oxide
fluorine doping
lithium-ion batteries
neutron total scattering