skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Structure Stabilization by Mixed Anions in Oxyfluoride Cathodes for High-Energy Lithium Batteries

Journal Article · · ACS Nano
 [1];  [2];  [3];  [3];  [4];  [3];  [2];  [2];  [2]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States); Korea Atomic Energy Research Institute, Daejeon (Korea)
  2. Rutgers Univ., New Brunswick, NJ (United States)
  3. State Univ. of New York at Binghampton, Binghampton, NY (United States)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States)
+ Show Author Affiliations

Mixed-anion oxyfluorides (i.e., FeOxF2-x) are an appealing alternative to pure fluorides as high-capacity cathodes in lithium batteries, with enhanced cyclability via oxygen substitution. Yet, it is still unclear how the mixed anions impact the local phase transformation and structural stability of oxyfluorides during cycling due to the complexity of electrochemical reactions, involving both lithium intercalation and conversion. Herein, we investigated the local chemical and structural ordering in FeO0.7F1.3 at length scales spanning from single particles to the bulk electrode, via a combination of electron spectrum-imaging, magnetization, electrochemistry, and synchrotron X-ray measurements. The FeO0.7F1.3 nanoparticles retain a FeF2-like rutile structure but chemically heterogeneous, with an F-rich core covered by thin O-rich shell. Upon lithiation the O-rich rutile phase is transformed into Li—Fe—O(—F) rocksalt that has high lattice coherency with converted metallic Fe, a feature that may facilitate the local electron and ion transport. The O-rich rocksalt is highly stable over lithiation/delithiation and thus advantageous to maintain the integrity of the particle, and due to its predominant distribution on the surface, it is expected to prevent the catalytic interaction of Fe with electrolyte. Our findings of the structural origin of cycling stability in oxyfluorides may provide insights into developing viable high-energy electrodes for lithium batteries.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012704; SC0001294
OSTI ID:
1239785
Report Number(s):
BNL-111677-2015-JA; YN0100000
Journal Information:
ACS Nano, Vol. 9, Issue 10; ISSN 1936-0851
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 43 works
Citation information provided by
Web of Science

References (33)

Carbon-Metal Fluoride Nanocomposites: Structure and Electrochemistry of FeF3 : C journal January 2003
Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries journal September 2000
Conversion reactions: a new pathway to realise energy in lithium-ion battery—review journal July 2008
Beyond Intercalation-Based Li-Ion Batteries: The State of the Art and Challenges of Electrode Materials Reacting Through Conversion Reactions journal August 2010
Fluoride based electrode materials for advanced energy storage devices journal April 2007
Li-Storage via Heterogeneous Reaction in Selected Binary Metal Fluorides and Oxides journal January 2004
Conversion Reaction Mechanisms in Lithium Ion Batteries: Study of the Binary Metal Fluoride Electrodes journal November 2011
Tracking lithium transport and electrochemical reactions in nanoparticles journal January 2012
Fabrication of FeF3 Nanoflowers on CNT Branches and Their Application to High Power Lithium Rechargeable Batteries journal October 2010
Effect of Vertically Structured Porosity on Electrochemical Performance of FeF2 Films for Lithium Batteries journal April 2014
Comprehensive Study of the CuF 2 Conversion Reaction Mechanism in a Lithium Ion Battery journal July 2014
Ternary metal fluorides as high-energy cathodes with low cycling hysteresis journal March 2015
Iron Oxyfluorides as High Capacity Cathode Materials for Lithium Batteries journal January 2009
Reversible Conversion Reactions with Lithium in Bismuth Oxyfluoride Nanocomposites journal January 2006
First-principles study of iron oxyfluorides and lithiation of FeOF journal March 2013
Synthesis of FeOF using roll-quenching method and the cathode properties for lithium-ion battery journal December 2013
Comprehensive Insights into the Structural and Chemical Changes in Mixed-Anion FeOF Electrodes by Using Operando PDF and NMR Spectroscopy
  • Wiaderek, Kamila M.; Borkiewicz, Olaf J.; Castillo-Martínez, Elizabeth
  • Journal of the American Chemical Society, Vol. 135, Issue 10 https://doi.org/10.1021/ja400229v
journal March 2013
Transport, Phase Reactions, and Hysteresis of Iron Fluoride and Oxyfluoride Conversion Electrode Materials for Lithium Batteries journal April 2014
Fe valence determination and Li elemental distribution in lithiated FeO0.7F1.3/C nanocomposite battery materials by electron energy loss spectroscopy (EELS) journal January 2012
Structural phase transformation and Fe valence evolution in FeOxF2−x/C nanocomposite electrodes during lithiation and de-lithiation processes journal January 2013
What can we learn about battery materials from their magnetic properties? journal January 2011
Heat Capacity and Entropy of FeF 2 and CoF 2 from 11 to 300°K. Thermal Anomalies Associated with Antiferromagnetic Ordering journal October 1955
High coercivity and superparamagnetic behavior of nanocrystalline iron particles in alumina matrix journal July 2001
Engineering nano-composite Li4Ti5O12 anodes via scanning electron-probe fabrication journal May 2013
Chemical Distribution and Bonding of Lithium in Intercalated Graphite: Identification with Optimized Electron Energy Loss Spectroscopy journal January 2011
Extraction of EELS white-line intensities of manganese compounds: Methods, accuracy, and valence sensitivity journal March 2006
Quantification of ferrous/ferric ratios in minerals: new evaluation schemes of Fe L 23 electron energy-loss near-edge spectra journal April 2002
High-Capacity Lithium-Ion Battery Conversion Cathodes Based on Iron Fluoride Nanowires and Insights into the Conversion Mechanism journal October 2012
Formation, dynamics, and implication of solid electrolyte interphase in high voltage reversible conversion fluoride nanocomposites journal January 2010
Synthesis and characterization of in situ Fe2O3-coated FeF3 cathode materials for rechargeable lithium batteries journal January 2012
Formation of Iron Oxyfluoride Phase on the Surface of Nano-Fe 3 O 4 Conversion Compound for Electrochemical Energy Storage journal October 2013
Controlled Formation of Mixed Nanoscale Domains of High Capacity Fe 2 O 3 –FeF 3 Conversion Compounds by Direct Fluorination journal February 2015
Energy storage in composites of a redox couple host and a lithium ion host journal June 2012

Cited By (14)

Insights into Ionic Transport and Structural Changes in Magnetite during Multiple-Electron Transfer Reactions journal March 2016
In‐situ structural characterizations of electrochemical intercalation of graphite compounds journal October 2019
Lithium-Iron Fluoride Battery with In Situ Surface Protection journal February 2016
Electrochemical properties of chromium oxyfluoride CrO 2−x F x with 0 ≤ x ≤ 0.3 journal January 2019
A critical review-promises and barriers of conversion electrodes for Li-ion batteries journal April 2017
Electrochemically driven conversion reaction in fluoride electrodes for energy storage devices journal April 2018
High energy-density and reversibility of iron fluoride cathode enabled via an intercalation-extrusion reaction journal June 2018
Lithium-free transition metal monoxides for positive electrodes in lithium-ion batteries journal January 2017
Atomistic Conversion Reaction Mechanism of WO 3 in Secondary Ion Batteries of Li, Na, and Ca journal April 2016
Three-dimensional iron oxyfluoride/N-doped carbon hybrid nanocomposites as high-performance cathodes for rechargeable Li-ion batteries journal January 2019
Defect-enriched iron fluoride-oxide nanoporous thin films bifunctional catalyst for water splitting journal May 2018
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
Investigating the Complex Chemistry of Functional Energy Storage Systems: The Need for an Integrative, Multiscale (Molecular to Mesoscale) Perspective journal April 2016

Similar Records

Microstructural Evolution Of Iron Oxyfluoride/Carbon Nanocomposites Upon Electrochemical Cycling
Journal Article · Thu Jun 16 00:00:00 EDT 2016 · Journal of Physical Chemistry. C · OSTI ID:1239785
+1 more
Origin of the High Capacity Manganese-Based Oxyfluoride Electrodes for Rechargeable Batteries
Journal Article · Tue Jul 17 00:00:00 EDT 2018 · Chemistry of Materials · OSTI ID:1239785
+7 more
Exploring the Origin of Anionic Redox Activity in Super Li-Rich Iron Oxide-Based High-Energy-Density Cathode Materials
Journal Article · Wed May 04 00:00:00 EDT 2022 · Chemistry of Materials · OSTI ID:1239785

Related Subjects

25 ENERGY STORAGE
lithium batteries
mixed-anion cathodes
iron oxyfluoride
scanning transmission electron microscopy (STEM)
electron energy loss spectroscopy (EELS)