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

Title: High Energy-Density and Reversibility of Iron Fluoride Cathode Enabled Via an Intercalation-Extrusion Reaction

Abstract

Iron fluoride, an intercalation-conversion cathode for lithium ion batteries, promises a high theoretical energy density of 1922 Wh Kg–1. However, poor electrochemical reversibility due to repeated breaking/reformation of metal-fluoride bonds poses a grand challenge for its practical application. Here we report that both a high reversibility over 1000 cycles and a high capacity of 420 mAh g–1 can be realized by concerted doping of cobalt and oxygen into iron fluoride. In the doped nanorods, an energy density of ~1000 Wh Kg–1 with a decay rate of 0.03% per cycle is achieved. The anion and cation’s co-substitutions thermodynamically reduce conversion-reaction potential and shift the reaction from less reversible intercalation-conversion reaction in iron fluoride to a highly reversible intercalation-extrusion reaction in doped material. Furthermore, the co-substitution strategy to tune the thermodynamic features of the reactions could be extended to other high energy conversion materials for improved performance.

Authors:
 [1]; ORCiD logo [2];  [1];  [1];  [1];  [2];  [3];  [2];  [1];  [1];  [1];  [2];  [2];  [1];  [4];  [2];  [1]
  1. Univ. of Maryland, College Park, MD (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. U.S. Army Research Lab., Adelphi, MD (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1436283
Alternate Identifier(s):
OSTI ID: 1767422
Report Number(s):
BNL-203611-2018-JAAM; BNL-221085-2021-JAAM
Journal ID: ISSN 2041-1723
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE

Citation Formats

Fan, Xiulin, Hu, Enyuan, Ji, Xiao, Zhu, Yizhou, Han, Fudong, Hwang, Sooyeon, Liu, Jue, Bak, Seongmin, Ma, Zhaohui, Gao, Tao, Liou, Sz -Chian, Bai, Jianming, Yang, Xiao -Qing, Mo, Yifei, Xu, Kang, Su, Dong, and Wang, Chunsheng. High Energy-Density and Reversibility of Iron Fluoride Cathode Enabled Via an Intercalation-Extrusion Reaction. United States: N. p., 2018. Web. https://doi.org/10.1038/s41467-018-04476-2.
Fan, Xiulin, Hu, Enyuan, Ji, Xiao, Zhu, Yizhou, Han, Fudong, Hwang, Sooyeon, Liu, Jue, Bak, Seongmin, Ma, Zhaohui, Gao, Tao, Liou, Sz -Chian, Bai, Jianming, Yang, Xiao -Qing, Mo, Yifei, Xu, Kang, Su, Dong, & Wang, Chunsheng. High Energy-Density and Reversibility of Iron Fluoride Cathode Enabled Via an Intercalation-Extrusion Reaction. United States. https://doi.org/10.1038/s41467-018-04476-2
Fan, Xiulin, Hu, Enyuan, Ji, Xiao, Zhu, Yizhou, Han, Fudong, Hwang, Sooyeon, Liu, Jue, Bak, Seongmin, Ma, Zhaohui, Gao, Tao, Liou, Sz -Chian, Bai, Jianming, Yang, Xiao -Qing, Mo, Yifei, Xu, Kang, Su, Dong, and Wang, Chunsheng. Wed . "High Energy-Density and Reversibility of Iron Fluoride Cathode Enabled Via an Intercalation-Extrusion Reaction". United States. https://doi.org/10.1038/s41467-018-04476-2. https://www.osti.gov/servlets/purl/1436283.
@article{osti_1436283,
title = {High Energy-Density and Reversibility of Iron Fluoride Cathode Enabled Via an Intercalation-Extrusion Reaction},
author = {Fan, Xiulin and Hu, Enyuan and Ji, Xiao and Zhu, Yizhou and Han, Fudong and Hwang, Sooyeon and Liu, Jue and Bak, Seongmin and Ma, Zhaohui and Gao, Tao and Liou, Sz -Chian and Bai, Jianming and Yang, Xiao -Qing and Mo, Yifei and Xu, Kang and Su, Dong and Wang, Chunsheng},
abstractNote = {Iron fluoride, an intercalation-conversion cathode for lithium ion batteries, promises a high theoretical energy density of 1922 Wh Kg–1. However, poor electrochemical reversibility due to repeated breaking/reformation of metal-fluoride bonds poses a grand challenge for its practical application. Here we report that both a high reversibility over 1000 cycles and a high capacity of 420 mAh g–1 can be realized by concerted doping of cobalt and oxygen into iron fluoride. In the doped nanorods, an energy density of ~1000 Wh Kg–1 with a decay rate of 0.03% per cycle is achieved. The anion and cation’s co-substitutions thermodynamically reduce conversion-reaction potential and shift the reaction from less reversible intercalation-conversion reaction in iron fluoride to a highly reversible intercalation-extrusion reaction in doped material. Furthermore, the co-substitution strategy to tune the thermodynamic features of the reactions could be extended to other high energy conversion materials for improved performance.},
doi = {10.1038/s41467-018-04476-2},
journal = {Nature Communications},
number = ,
volume = 9,
place = {United States},
year = {2018},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 8 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Fabrication of FeF3 Nanoflowers on CNT Branches and Their Application to High Power Lithium Rechargeable Batteries
journal, October 2010

  • Kim, Sung-Wook; Seo, Dong-Hwa; Gwon, Hyeokjo
  • Advanced Materials, Vol. 22, Issue 46
  • DOI: 10.1002/adma.201002879

Three-dimensionally ordered macroporous FeF3 and its in situ homogenous polymerization coating for high energy and power density lithium ion batteries
journal, January 2012

  • Ma, De-long; Cao, Zhan-yi; Wang, Heng-guo
  • Energy & Environmental Science, Vol. 5, Issue 9
  • DOI: 10.1039/c2ee22568a

Projector augmented-wave method
journal, December 1994


PDFgetX3 : a rapid and highly automatable program for processing powder diffraction data into total scattering pair distribution functions
journal, March 2013


Future generations of cathode materials: an automotive industry perspective
journal, January 2015

  • Andre, Dave; Kim, Sung-Jin; Lamp, Peter
  • Journal of Materials Chemistry A, Vol. 3, Issue 13
  • DOI: 10.1039/C5TA00361J

First-principles study of iron oxyfluorides and lithiation of FeOF
journal, March 2013


Mesoscale Effects in Electrochemical Conversion: Coupling of Chemistry to Atomic- and Nanoscale Structure in Iron-Based Electrodes
journal, April 2014

  • Wiaderek, Kamila M.; Borkiewicz, Olaf J.; Pereira, Nathalie
  • Journal of the American Chemical Society, Vol. 136, Issue 17
  • DOI: 10.1021/ja501854y

Origins of Large Voltage Hysteresis in High-Energy-Density Metal Fluoride Lithium-Ion Battery Conversion Electrodes
journal, February 2016

  • Li, Linsen; Jacobs, Ryan; Gao, Peng
  • Journal of the American Chemical Society, Vol. 138, Issue 8
  • DOI: 10.1021/jacs.6b00061

VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011


First-Principles Investigation of the Li−Fe−F Phase Diagram and Equilibrium and Nonequilibrium Conversion Reactions of Iron Fluorides with Lithium
journal, August 2008

  • Doe, Robert E.; Persson, Kristin A.; Meng, Y. Shirley
  • Chemistry of Materials, Vol. 20, Issue 16
  • DOI: 10.1021/cm801105p

Sodiation via Heterogeneous Disproportionation in FeF 2 Electrodes for Sodium-Ion Batteries
journal, June 2014

  • He, Kai; Zhou, Yongning; Gao, Peng
  • ACS Nano, Vol. 8, Issue 7
  • DOI: 10.1021/nn502284y

Modified synthesis of [Fe/LiF/C] nanocomposite, and its application as conversion cathode material in lithium batteries
journal, July 2011


Single-Layered Ultrasmall Nanoplates of MoS 2 Embedded in Carbon Nanofibers with Excellent Electrochemical Performance for Lithium and Sodium Storage
journal, January 2014

  • Zhu, Changbao; Mu, Xiaoke; van Aken, Peter A.
  • Angewandte Chemie International Edition, Vol. 53, Issue 8
  • DOI: 10.1002/anie.201308354

High-Capacity Lithium-Ion Battery Conversion Cathodes Based on Iron Fluoride Nanowires and Insights into the Conversion Mechanism
journal, October 2012

  • Li, Linsen; Meng, Fei; Jin, Song
  • Nano Letters, Vol. 12, Issue 11, p. 6030-6037
  • DOI: 10.1021/nl303630p

Investigation of SEI Layer Formation in Conversion Iron Fluoride Cathodes by Combined STEM/EELS and XPS
journal, April 2015

  • Sina, M.; Thorpe, R.; Rangan, S.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 18
  • DOI: 10.1021/acs.jpcc.5b02058

In Situ Chemical Synthesis of Lithium Fluoride/Metal Nanocomposite for High Capacity Prelithiation of Cathodes
journal, January 2016


Iron Oxyfluorides as High Capacity Cathode Materials for Lithium Batteries
journal, January 2009

  • Pereira, N.; Badway, F.; Wartelsky, M.
  • Journal of The Electrochemical Society, Vol. 156, Issue 6, p. A407-A416
  • DOI: 10.1149/1.3106132

In situ lithiated FeF3/C nanocomposite as high energy conversion-reaction cathode for lithium-ion batteries
journal, March 2016


Investigation of the Conversion Reaction Mechanisms for Binary Copper(II) Compounds by Solid-State NMR Spectroscopy and X-ray Diffraction
journal, July 2009

  • Yamakawa, Naoko; Jiang, Meng; Grey, Clare P.
  • Chemistry of Materials, Vol. 21, Issue 14
  • DOI: 10.1021/cm900581b

CFx Derived Carbon-FeF 2 Nanocomposites for Reversible Lithium Storage
journal, December 2012

  • Reddy, M. Anji; Breitung, Ben; Chakravadhanula, Venkata Sai Kiran
  • Advanced Energy Materials, Vol. 3, Issue 3
  • DOI: 10.1002/aenm.201200788

Structure and Electrochemistry of Carbon-Metal Fluoride Nanocomposites Fabricated by Solid-State Redox Conversion Reaction
journal, January 2005

  • Plitz, I.; Badway, F.; Al-Sharab, J.
  • Journal of The Electrochemical Society, Vol. 152, Issue 2, p. A307-A315
  • DOI: 10.1149/1.1842035

Ultimate Limits to Intercalation Reactions for Lithium Batteries
journal, October 2014

  • Whittingham, M. Stanley
  • Chemical Reviews, Vol. 114, Issue 23
  • DOI: 10.1021/cr5003003

Comprehensive Insights into the Structural and Chemical Changes in Mixed-Anion FeOF Electrodes by Using Operando PDF and NMR Spectroscopy
journal, March 2013

  • Wiaderek, Kamila M.; Borkiewicz, Olaf J.; Castillo-Martínez, Elizabeth
  • Journal of the American Chemical Society, Vol. 135, Issue 10
  • DOI: 10.1021/ja400229v

PEDOT Encapsulated FeOF Nanorod Cathodes for High Energy Lithium-Ion Batteries
journal, October 2015


A High-Capacity Cathode for Lithium Batteries Consisting of Porous Microspheres of Highly Amorphized Iron Fluoride Densified from Its Open Parent Phase
journal, August 2012

  • Li, Chilin; Mu, Xiaoke; van Aken, Peter A.
  • Advanced Energy Materials, Vol. 3, Issue 1
  • DOI: 10.1002/aenm.201200209

Wet-Chemical Synthesis of Phase-Pure FeOF Nanorods as High-Capacity Cathodes for Sodium-Ion Batteries
journal, January 2015


Carbon Metal Fluoride Nanocomposites: High-Capacity Reversible Metal Fluoride Conversion Materials as Rechargeable Positive Electrodes for Li Batteries
journal, January 2003

  • Badway, F.; Cosandey, F.; Pereira, N.
  • Journal of The Electrochemical Society, Vol. 150, Issue 10, p. A1318-A1327
  • DOI: 10.1149/1.1602454

Synthesis and characterization of in situ Fe2O3-coated FeF3 cathode materials for rechargeable lithium batteries
journal, January 2012

  • Zhang, Wei; Ma, Lin; Yue, Hongjun
  • Journal of Materials Chemistry, Vol. 22, Issue 47
  • DOI: 10.1039/c2jm34391f

Electrochemical Cycling and Lithium Insertion in Nanostructured FeF 3 Cathodes
journal, December 2013

  • Tan, H. J.; Smith, Hillary L.; Kim, L.
  • Journal of The Electrochemical Society, Vol. 161, Issue 3
  • DOI: 10.1149/2.096403jes

Comprehensive Study of the CuF 2 Conversion Reaction Mechanism in a Lithium Ion Battery
journal, July 2014

  • Hua, Xiao; Robert, Rosa; Du, Lin-Shu
  • The Journal of Physical Chemistry C, Vol. 118, Issue 28
  • DOI: 10.1021/jp503902z

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Challenges in the development of advanced Li-ion batteries: a review
journal, January 2011

  • Etacheri, Vinodkumar; Marom, Rotem; Elazari, Ran
  • Energy & Environmental Science, Vol. 4, Issue 9
  • DOI: 10.1039/c1ee01598b

Thermodynamics and Kinetics of the Li/FeF 3 Reaction by Electrochemical Analysis
journal, February 2012

  • Liu, Ping; Vajo, John J.; Wang, John S.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 10
  • DOI: 10.1021/jp211927g

Transport, Phase Reactions, and Hysteresis of Iron Fluoride and Oxyfluoride Conversion Electrode Materials for Lithium Batteries
journal, April 2014

  • Ko, Jonathan K.; Wiaderek, Kamila M.; Pereira, Nathalie
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 14
  • DOI: 10.1021/am500538b

Carbon-Metal Fluoride Nanocomposites: Structure and Electrochemistry of FeF3 : C
journal, January 2003

  • Badway, F.; Pereira, N.; Cosandey, F.
  • Journal of The Electrochemical Society, Vol. 150, Issue 9, p. A1209-A1218
  • DOI: 10.1149/1.1596162

Formation of lithium fluoride/metal nanocomposites for energy storage through solid state reduction of metal fluorides
journal, December 2011


Li−Fe−P−O 2 Phase Diagram from First Principles Calculations
journal, February 2008

  • Ong, Shyue Ping; Wang, Lei; Kang, Byoungwoo
  • Chemistry of Materials, Vol. 20, Issue 5
  • DOI: 10.1021/cm702327g

A reversible copper extrusion–insertion electrode for rechargeable Li batteries
journal, October 2003

  • Morcrette, M.; Rozier, P.; Dupont, L.
  • Nature Materials, Vol. 2, Issue 11
  • DOI: 10.1038/nmat1002

PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals
journal, July 2007


Nanoscale Stabilization of Sodium Oxides: Implications for Na–O 2 Batteries
journal, January 2014

  • Kang, ShinYoung; Mo, Yifei; Ong, Shyue Ping
  • Nano Letters, Vol. 14, Issue 2
  • DOI: 10.1021/nl404557w

Calculations of Li-Ion Diffusion in Olivine Phosphates
journal, September 2011

  • Dathar, Gopi Krishna Phani; Sheppard, Daniel; Stevenson, Keith J.
  • Chemistry of Materials, Vol. 23, Issue 17
  • DOI: 10.1021/cm201604g

Origin of additional capacities in metal oxide lithium-ion battery electrodes
journal, November 2013

  • Hu, Yan-Yan; Liu, Zigeng; Nam, Kyung-Wan
  • Nature Materials, Vol. 12, Issue 12
  • DOI: 10.1038/nmat3784

Nanostructured materials for advanced energy conversion and storage devices
journal, May 2005

  • Aricò, Antonino Salvatore; Bruce, Peter; Scrosati, Bruno
  • Nature Materials, Vol. 4, Issue 5, p. 366-377
  • DOI: 10.1038/nmat1368

Conversion Reaction Mechanisms in Lithium Ion Batteries: Study of the Binary Metal Fluoride Electrodes
journal, November 2011

  • Wang, Feng; Robert, Rosa; Chernova, Natasha A.
  • Journal of the American Chemical Society, Vol. 133, Issue 46
  • DOI: 10.1021/ja206268a

Atomistic Insights into the Conversion Reaction in Iron Fluoride: A Dynamically Adaptive Force Field Approach
journal, April 2012

  • Ma, Ying; Garofalini, Stephen H.
  • Journal of the American Chemical Society, Vol. 134, Issue 19
  • DOI: 10.1021/ja301637c

Fabrication of FeF3 nanocrystals dispersed into a porous carbon matrix as a high performance cathode material for lithium ion batteries
journal, January 2013

  • Ma, Ruguang; Wang, Man; Tao, Pengpeng
  • Journal of Materials Chemistry A, Vol. 1, Issue 47
  • DOI: 10.1039/c3ta13086j

Synthesis of FeOF using roll-quenching method and the cathode properties for lithium-ion battery
journal, December 2013


Supercritical-fluid synthesis of FeF2 and CoF2 Li-ion conversion materials
journal, January 2013

  • Armstrong, Mark J.; Panneerselvam, Arunkumar; O'Regan, Colm
  • Journal of Materials Chemistry A, Vol. 1, Issue 36
  • DOI: 10.1039/c3ta12436c

Pomegranate-Structured Conversion-Reaction Cathode with a Built-in Li Source for High-Energy Li-Ion Batteries
journal, May 2016


Electron Energy Loss Spectroscopy Study of Li in Lithiated FeOF/C Nanocomposite Battery Materials
journal, July 2010


Structural phase transformation and Fe valence evolution in FeOxF2−x/C nanocomposite electrodes during lithiation and de-lithiation processes
journal, January 2013

  • Sina, M.; Nam, K. -W.; Su, D.
  • Journal of Materials Chemistry A, Vol. 1, Issue 38
  • DOI: 10.1039/c3ta12109g

Surface energies of elemental crystals
journal, September 2016

  • Tran, Richard; Xu, Zihan; Radhakrishnan, Balachandran
  • Scientific Data, Vol. 3, Issue 1
  • DOI: 10.1038/sdata.2016.80

Rationale for mixing exact exchange with density functional approximations
journal, December 1996

  • Perdew, John P.; Ernzerhof, Matthias; Burke, Kieron
  • The Journal of Chemical Physics, Vol. 105, Issue 22, p. 9982-9985
  • DOI: 10.1063/1.472933

Improvement of Cycling Performance of FeF 3 -Based Lithium-Ion Battery by Boron-Based Additives
journal, January 2016

  • Kumagae, Kiyoshi; Okazaki, Ken-ichi; Matsui, Keitaro
  • Journal of The Electrochemical Society, Vol. 163, Issue 8
  • DOI: 10.1149/2.0871608jes

Structure Stabilization by Mixed Anions in Oxyfluoride Cathodes for High-Energy Lithium Batteries
journal, September 2015


Fityk : a general-purpose peak fitting program
journal, September 2010


Two-dimensional detector software: From real detector to idealised image or two-theta scan
journal, January 1996

  • Hammersley, A. P.; Svensson, S. O.; Hanfland, M.
  • High Pressure Research, Vol. 14, Issue 4-6, p. 235-248
  • DOI: 10.1080/08957959608201408

Metal Fluorides Nanoconfined in Carbon Nanopores as Reversible High Capacity Cathodes for Li and Li-Ion Rechargeable Batteries: FeF 2 as an Example
journal, February 2015

  • Gu, Wentian; Magasinski, Alexandre; Zdyrko, Bogdan
  • Advanced Energy Materials, Vol. 5, Issue 4
  • DOI: 10.1002/aenm.201500243

Wet-Chemical Synthesis of Phase-Pure FeOF Nanorods as High-Capacity Cathodes for Sodium-Ion Batteries
journal, January 2015


Tracking lithium transport and electrochemical reactions in nanoparticles
journal, January 2012

  • Wang, Feng; Yu, Hui-Chia; Chen, Min-Hua
  • Nature Communications, Vol. 3, Issue 1
  • DOI: 10.1038/ncomms2185

Ternary metal fluorides as high-energy cathodes with low cycling hysteresis
journal, March 2015

  • Wang, Feng; Kim, Sung-Wook; Seo, Dong-Hwa
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7668

Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect
journal, February 2020


Lead palladium titanate: A room temperature nanoscale multiferroic thin film
journal, February 2020


    Works referencing / citing this record:

    3D Honeycomb Architecture Enables a High‐Rate and Long‐Life Iron (III) Fluoride–Lithium Battery
    journal, September 2019

    • Wu, Feixiang; Srot, Vesna; Chen, Shuangqiang
    • Advanced Materials, Vol. 31, Issue 43
    • DOI: 10.1002/adma.201905146

    3D Starfish‐Like FeOF on Graphene Sheets: Engineered Synthesis and Lithium Storage Performance
    journal, May 2019

    • Zhai, Jingru; Lei, Zhengyu; Sun, Kening
    • Chemistry – A European Journal, Vol. 25, Issue 32
    • DOI: 10.1002/chem.201900948

    Phase evolution of conversion-type electrode for lithium ion batteries
    journal, May 2019


    Controlled synthesis of ammonium manganese tri-fluoride nanoparticles with enhanced electrochemical performance
    journal, April 2019

    • Khan, Jamshid; Ullah, Hameed; Sajjad, Muhammad
    • Materials Research Express, Vol. 6, Issue 7
    • DOI: 10.1088/2053-1591/ab18bb

    Self-Templated Formation of Hollow Yolk-Like Spheres Iron Fluoride as Cathode Material for High-Performance Li-Ion Batteries
    journal, January 2019

    • Lin, Jinfang; Zhu, Licai; Chen, Shuyi
    • Journal of The Electrochemical Society, Vol. 166, Issue 10
    • DOI: 10.1149/2.0991910jes