Structural phase transformation and Fe valence evolution in FeOxF2-x/C nanocomposite electrodes during lithiation and de-lithiation processes

Sina, M.; Nam, K. -W.; Su, D.; Pereira, N.; Yang, X. -Q.; Amatucci, G. G.; Cosandey, F.

doi:10.1039/C3TA12109G

Structural phase transformation and Fe valence evolution in FeOxF2-x/C nanocomposite electrodes during lithiation and de-lithiation processes

Journal Article · Tue Jan 01 04:00:00 EST 2013 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/C3TA12109G· OSTI ID:1382483

Sina, M.; Nam, K. -W.; Su, D.; Pereira, N.; Yang, X. -Q.; Amatucci, G. G.; Cosandey, F.

In this study, the structural changes of FeOxF2-x/C during the first discharge and recharge cycles were studied by ex situ electron microscopy techniques including annular dark field scanning transmission electron microscopy (DF-STEM) imaging, selected area electron diffraction (SAED) and electron energy loss spectroscopy (EELS) as well as by in situ X-ray absorption spectroscopy (XAS). The evolution of the valence state of Fe was determined by combined EELS using the Fe-L edge and XAS using the Fe-K edge. The results of this investigation show that the conversion reaction path during 1st lithiation is very different from the re-conversion path during 1st delithiation. During lithiation, intercalation is first observed followed by conversion into a lithiated rocksalt (Li–Fe–O–F) structure, and metallic Fe and LiF phases. During delithiation, the rocksalt phase does not disappear, but co-exists with an amorphous (rutile type) phase formed initially by the reaction of LiF and Fe. However, a de-intercalation stage is still observed at the end of reconversion similar to a single phase process despite the coexistence of these two (rocksalt and amorphous) phases.

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES)

Sponsoring Organization:: USDOE SC Office of Basic Energy Sciences (SC-22)

DOE Contract Number:: SC0001294

OSTI ID:: 1382483

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 38 Vol. 1; ISSN JMCAET; ISSN 2050-7488

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

References (36)

Investigation of the Lithiation and Delithiation Conversion Mechanisms of Bismuth Fluoride Nanocomposites Bervas, M.; Mansour, A. N.; Yoon, W.-S. Journal of The Electrochemical Society, Vol. 153, Issue 4, p. A799-A808 https://doi.org/10.1149/1.2167951	journal	January 2006
Atomistic Insights into the Conversion Reaction in Iron Fluoride: A Dynamically Adaptive Force Field Approach Ma, Ying; Garofalini, Stephen H. Journal of the American Chemical Society, Vol. 134, Issue 19 https://doi.org/10.1021/ja301637c	journal	April 2012
EELS Spectroscopy of Iron Fluorides and FeF_x/C Nanocomposite Electrodes Used in Li-Ion Batteries Cosandey, Frederic; Al-Sharab, Jafar F.; Badway, Fadwa Microscopy and Microanalysis, Vol. 13, Issue 02, p. 87-95 https://doi.org/10.1017/S1431927607070183	journal	February 2007
High-Capacity Lithium-Ion Battery Conversion Cathodes Based on Iron Fluoride Nanowires and Insights into the Conversion Mechanism Li, Linsen; Meng, Fei; Jin, Song Nano Letters, Vol. 12, Issue 11, p. 6030-6037 https://doi.org/10.1021/nl303630p	journal	October 2012
Electron‐beam induced crystallization transition in self‐developing amorphous AlF ₃ resists Chen, G. S.; Boothroyd, C. B.; Humphreys, C. J. Applied Physics Letters, Vol. 69, Issue 2 https://doi.org/10.1063/1.117361	journal	July 1996
Transmission electron microscopy and electron diffraction study of the short-range ordering structure of α-LiFeO ₂ Mitome, Masanori; Kohiki, Shigemi; Murakawa, Yusuke Acta Crystallographica Section B Structural Science, Vol. 60, Issue 6 https://doi.org/10.1107/S0108768104023456	journal	November 2004
Electron energy loss spectroscopy studies of the amorphous to crystalline transition in FeF3 Saifullah, M. S. M.; Botton, G. A.; Boothroyd, C. B. Journal of Applied Physics, Vol. 86, Issue 5 https://doi.org/10.1063/1.371083	journal	September 1999
Positive Electrode Materials for Li-Ion and Li-Batteries ^† Ellis, Brian L.; Lee, Kyu Tae; Nazar, Linda F. Chemistry of Materials, Vol. 22, Issue 3 https://doi.org/10.1021/cm902696j	journal	February 2010
Challenges for Rechargeable Li Batteries Goodenough, John B.; Kim, Youngsik Chemistry of Materials, Vol. 22, Issue 3, p. 587-603 https://doi.org/10.1021/cm901452z	journal	February 2010
Iron Oxyfluorides as High Capacity Cathode Materials for Lithium Batteries Pereira, N.; Badway, F.; Wartelsky, M. Journal of The Electrochemical Society, Vol. 156, Issue 6, p. A407-A416 https://doi.org/10.1149/1.3106132	journal	January 2009
Quantitative determination of iron oxidation states in minerals using Fe L 2,3 -edge electron energy-loss near-edge structure spectroscopy van Aken, P. A.; Liebscher, B.; Styrsa, V. J. Physics and Chemistry of Minerals, Vol. 25, Issue 5 https://doi.org/10.1007/s002690050122	journal	May 1998
Identifying the Local Structures Formed during Lithiation of the Conversion Material, Iron Fluoride, in a Li Ion Battery: A Solid-State NMR, X-ray Diffraction, and Pair Distribution Function Analysis Study Yamakawa, Naoko; Jiang, Meng; Key, Baris Journal of the American Chemical Society, Vol. 131, Issue 30 https://doi.org/10.1021/ja902639w	journal	August 2009
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
The investigation on electrochemical reaction mechanism of CuF2 thin film with lithium Cui, Yan-Hua; Xue, Ming-Zhe; Zhou, Yong-Ning Electrochimica Acta, Vol. 56, Issue 5 https://doi.org/10.1016/j.electacta.2010.12.014	journal	February 2011
Fe valence determination and Li elemental distribution in lithiated FeO0.7F1.3/C nanocomposite battery materials by electron energy loss spectroscopy (EELS) Cosandey, F.; Su, D.; Sina, M. Micron, Vol. 43, Issue 1 https://doi.org/10.1016/j.micron.2011.05.009	journal	January 2012
Structure and Electrochemistry of Copper Fluoride Nanocomposites Utilizing Mixed Conducting Matrices Badway, F.; Mansour, A. N.; Pereira, N. Chemistry of Materials, Vol. 19, Issue 17, p. 4129-4141 https://doi.org/10.1021/cm070421g	journal	August 2007
An Electron Diffraction and Crystal Chemical Investigation of Oxygen/Fluorine Ordering in Rutile-Type Iron Oxyfluoride, FeOF Brink, Frank J.; Withers, Ray L.; Thompson, John G. Journal of Solid State Chemistry, Vol. 155, Issue 2 https://doi.org/10.1006/jssc.2000.8925	journal	December 2000
Reversible Three-Electron Redox Behaviors of FeF ₃ Nanocrystals as High-Capacity Cathode-Active Materials for Li-Ion Batteries Li, Ting; Li, Lei; Cao, Yu L. The Journal of Physical Chemistry C, Vol. 114, Issue 7 https://doi.org/10.1021/jp908741d	journal	January 2010
Carbon-Metal Fluoride Nanocomposites: Structure and Electrochemistry of FeF₃ : C Badway, F.; Pereira, N.; Cosandey, F. Journal of The Electrochemical Society, Vol. 150, Issue 9, p. A1209-A1218 https://doi.org/10.1149/1.1596162	journal	January 2003
An Electron Energy-Loss Spectrometry Study of Charge Compensation in LiNi _0.8 Co _0.2 O ₂ Graetz, J.; Ahn, C. C.; Yazami, R. The Journal of Physical Chemistry B, Vol. 107, Issue 13 https://doi.org/10.1021/jp026484y	journal	April 2003
Formation, dynamics, and implication of solid electrolyte interphase in high voltage reversible conversion fluoride nanocomposites Gmitter, Andrew J.; Badway, Fadwa; Rangan, Sylvie Journal of Materials Chemistry, Vol. 20, Issue 20 https://doi.org/10.1039/b923908a	journal	January 2010
Beyond Intercalation-Based Li-Ion Batteries: The State of the Art and Challenges of Electrode Materials Reacting Through Conversion Reactions Cabana, Jordi; Monconduit, Laure; Larcher, Dominique Advanced Materials, Vol. 22, Issue 35 https://doi.org/10.1002/adma.201000717	journal	August 2010
First-principles study of iron oxyfluorides and lithiation of FeOF Chevrier, Vincent L.; Hautier, Geoffroy; Ong, Shyue Ping Physical Review B, Vol. 87, Issue 9 https://doi.org/10.1103/PhysRevB.87.094118	journal	March 2013
Bismuth Fluoride Nanocomposite as a Positive Electrode Material for Rechargeable Lithium Batteries Bervas, M.; Badway, F.; Klein, L. C. Electrochemical and Solid-State Letters, Vol. 8, Issue 4, p. A179-A183 https://doi.org/10.1149/1.1861040	journal	January 2005
Reversible Formation and Decomposition of LiF Clusters Using Transition Metal Fluorides as Precursors and Their Application in Rechargeable Li Batteries Li, H.; Richter, G.; Maier, J. Advanced Materials, Vol. 15, Issue 9 https://doi.org/10.1002/adma.200304574	journal	May 2003
Lithium Batteries and Cathode Materials Whittingham, M. Stanley Chemical Reviews, Vol. 104, Issue 10, p. 4271-4302 https://doi.org/10.1021/cr020731c	journal	October 2004
Pulsed laser deposited iron fluoride thin films for lithium-ion batteries Makimura, Yoshinari; Rougier, Aline; Tarascon, Jean-Marie Applied Surface Science, Vol. 252, Issue 13 https://doi.org/10.1016/j.apsusc.2005.06.043	journal	April 2006
Conversion Reaction of FeF ₂ Thin Films upon Exposure to Atomic Lithium Rangan, Sylvie; Thorpe, Ryan; Bartynski, Robert Allen The Journal of Physical Chemistry C, Vol. 116, Issue 19 https://doi.org/10.1021/jp300669d	journal	May 2012
Carbon Metal Fluoride Nanocomposites: High-Capacity Reversible Metal Fluoride Conversion Materials as Rechargeable Positive Electrodes for Li Batteries Badway, F.; Cosandey, F.; Pereira, N. Journal of The Electrochemical Society, Vol. 150, Issue 10, p. A1318-A1327 https://doi.org/10.1149/1.1602454	journal	January 2003
Reversible lithium storage in LiF/Ti nanocomposites Yu, X. Q.; Sun, J. P.; Tang, K. Physical Chemistry Chemical Physics, Vol. 11, Issue 41 https://doi.org/10.1039/b908149f	journal	January 2009
A ferrocene-based carbon–iron lithium fluoride nanocomposite as a stable electrode material in lithium batteries Prakash, Raju; Mishra, Ajay Kumar; Roth, Arne Journal of Materials Chemistry, Vol. 20, Issue 10 https://doi.org/10.1039/b919097j	journal	January 2010
Fluoride based electrode materials for advanced energy storage devices Amatucci, Glenn G.; Pereira, Nathalie Journal of Fluorine Chemistry, Vol. 128, Issue 4, p. 243-262 https://doi.org/10.1016/j.jfluchem.2006.11.016	journal	April 2007
Investigation of the Conversion Reaction Mechanisms for Binary Copper(II) Compounds by Solid-State NMR Spectroscopy and X-ray Diffraction Yamakawa, Naoko; Jiang, Meng; Grey, Clare P. Chemistry of Materials, Vol. 21, Issue 14 https://doi.org/10.1021/cm900581b	journal	July 2009
First-Principles Investigation of the Li−Fe−F Phase Diagram and Equilibrium and Nonequilibrium Conversion Reactions of Iron Fluorides with Lithium Doe, Robert E.; Persson, Kristin A.; Meng, Y. Shirley Chemistry of Materials, Vol. 20, Issue 16 https://doi.org/10.1021/cm801105p	journal	August 2008
Electron Diffraction Based Analysis of Phase Fractions and Texture in Nanocrystalline Thin Films, Part III: Application Examples Lábár, J. L.; Adamik, M.; Barna, B. P. Microscopy and Microanalysis, Vol. 18, Issue 2 https://doi.org/10.1017/S1431927611012803	journal	March 2012
Conversion Reaction Mechanisms in Lithium Ion Batteries: Study of the Binary Metal Fluoride Electrodes Wang, Feng; Robert, Rosa; Chernova, Natasha A. Journal of the American Chemical Society, Vol. 133, Issue 46 https://doi.org/10.1021/ja206268a	journal	November 2011

Similar Records

Microstructural Evolution Of Iron Oxyfluoride/Carbon Nanocomposites Upon Electrochemical Cycling

Journal Article · Wed Jun 15 20:00:00 EDT 2016 · Journal of Physical Chemistry. C · OSTI ID:1387881

Investigation of the Lithiation and Delithiation Conversion Mechanisms of Bismuth Fluoride Nanocomposites

Journal Article · Sat Dec 31 23:00:00 EST 2005 · J. Electrochem. Soc. · OSTI ID:914117

Revealing Reaction Pathways of Collective Substituted Iron Fluoride Electrode for Lithium Ion Batteries

Journal Article · Tue Jul 07 20:00:00 EDT 2020 · ACS Nano · OSTI ID:1638818

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
charge transport
defects
energy storage (including batteries and capacitors)
materials and chemistry by design
synthesis (novel materials)

Structural phase transformation and Fe valence evolution in FeOxF2-x/C nanocomposite electrodes during lithiation and de-lithiation processes

Citation Formats

References (36)

Similar Records

Related Subjects