Liquid Phase Exfoliation of Nonlayered Non-Van Der Waals Iron Trifluoride (FeF 3) into 2D-Platelets for High-Capacity Lithium Storing Cathodes

Developing high-performance cathode materials for lithium-ion batteries is necessary to maximise both energy and power density. One promising cathode material is iron trifluoride (FeF 3 ) having a high theoretical capacity of 712 mAh/g, although achieving this value experimentally is challenging. Our previous works has shown that achievable capacity can be maximised when active materials are in a two-dimensional (2D) form. Liquid-phase exfoliation (LPE) method seems intuitively inappropriate to produce 2D-platelets from non-layered non-Van der Waals (non-VdW) bulk materials. However, in this manuscript, we show that bulk non-layered non-VdW material, FeF 3 can be converted from its 3D form to quasi-2D platelets. The XRD, TEM and elemental analysis showed the structure and stoichiometry of these platelets to be similar to that of bulk material. Interestingly, although AFM showed majority of platelets to be quasi-2D, it revealed the platelet aspect-ratio to be thickness dependent, falling from ~12 for the thinnest platelets to ~1 for the thickest ones. Lithium storage experiments showed that, once coated in carbon and mixed with single walled nanotubes, FeF 3 platelets display good Li storage capability coupled with reasonable stability. At very low currents, this material displays an active-mass normalised capacity of ~700 mAh/g, very close to the theoretical value. However, the capacity fell off at higher currents with detailed analysis implying FeF 3 cathodes in general to display poor rate performance due to low ionic diffusivity.

[1]  J. Coleman,et al.  2D nanosheets from fool’s gold by LPE: High performance lithium-ion battery anodes made from stone , 2021, FlatChem.

[2]  Yu. G. Kubarev,et al.  ELECTRICAL , 2021, Data Center Handbook.

[3]  M. Pasta,et al.  Conversion-Type Fluoride Cathodes: Current State of the Art , 2021 .

[4]  J. Shapter,et al.  Recent progress of advanced anode materials of lithium-ion batteries , 2021 .

[5]  Q. Ramasse,et al.  Exfoliation of Alpha‐Germanium: A Covalent Diamond‐Like Structure , 2021, Advanced materials.

[6]  P. Midgley,et al.  Revisiting metal fluorides as lithium-ion battery cathodes , 2021, Nature Materials.

[7]  Qing Hua Wang,et al.  Exfoliation of boron carbide into ultrathin nanosheets. , 2021, Nanoscale.

[8]  J. Coleman,et al.  Liquid Exfoliated SnP3 Nanosheets for Very High Areal Capacity Lithium‐Ion Batteries , 2020, Advanced Energy Materials.

[9]  C. Futalan,et al.  MOF-derived FeF2 nanoparticles@graphitic carbon undergoing in situ phase transformation to FeF3 as a superior sodium-ion cathode material , 2020 .

[10]  J. Coleman,et al.  Production of Quasi-2D Platelets of Non-Layered Iron Pyrite (FeS2) by Liquid-Phase Exfoliation for High Performance Battery Electrodes. , 2020, ACS nano.

[11]  A. A. Anappara,et al.  Facile synthesis of aqueous-dispersed luminescent nanosheets from non-layered lanthanum hexaboride , 2020, RSC advances.

[12]  Bingkun Guo,et al.  An Overview on the Advances of LiCoO2 Cathodes for Lithium‐Ion Batteries , 2020, Advanced Energy Materials.

[13]  Yanguang Li,et al.  Liquid phase exfoliation of GeS nanosheets in ambient conditions for lithium ion battery applications , 2020, 2D Materials.

[14]  J. Coleman,et al.  The Rate Performance of 2D Material-Based Battery Electrodes May Not Be As Good as Is Commonly Believed. , 2020, ACS nano.

[15]  Ruiyuan Tian,et al.  Developing models to fit capacity–rate data in battery systems , 2019, Current Opinion in Electrochemistry.

[16]  Liquan Chen,et al.  Li-free Cathode Materials for High Energy Density Lithium Batteries , 2019, Joule.

[17]  Feixiang Wu,et al.  3D Honeycomb Architecture Enables a High‐Rate and Long‐Life Iron (III) Fluoride–Lithium Battery , 2019, Advanced materials.

[18]  G. Yushin,et al.  Cycle stability of conversion-type iron fluoride lithium battery cathode at elevated temperatures in polymer electrolyte composites , 2019, Nature Materials.

[19]  Jian Sun,et al.  Enhanced supercapacitive performance of novel ultrathin SiC nanosheets directly by liquid phase exfoliation , 2019, Inorganic Chemistry Communications.

[20]  R. E. Schaak,et al.  Tutorial on Powder X-ray Diffraction for Characterizing Nanoscale Materials. , 2019, ACS nano.

[21]  J. Coleman,et al.  High areal capacity battery electrodes enabled by segregated nanotube networks , 2019, Nature Energy.

[22]  J. Coleman,et al.  Equipartition of Energy Defines the Size-Thickness Relationship in Liquid-Exfoliated Nanosheets. , 2019, ACS nano.

[23]  P. Lu,et al.  Cryogenic Exfoliation of Non-layered Magnesium into Two-Dimensional Crystals. , 2019, Angewandte Chemie.

[24]  J. Coleman,et al.  Solvent exfoliation stabilizes TiS2 nanosheets against oxidation, facilitating lithium storage applications. , 2019, Nanoscale.

[25]  Chen Lu,et al.  Improved rate and cycling performance of FeF2-rGO hybrid cathode with poly (acrylic acid) binder for sodium ion batteries , 2019, Journal of Power Sources.

[26]  Zhengping Wang,et al.  Liquid-Phase Exfoliated Silicon Nanosheets: Saturable Absorber for Solid-State Lasers , 2019, Materials.

[27]  M. Salanne,et al.  Impact of Anion Vacancies on the Local and Electronic Structures of Iron-Based Oxyfluoride Electrodes. , 2018, The journal of physical chemistry letters.

[28]  J. Coleman,et al.  Non-resonant light scattering in dispersions of 2D nanosheets , 2018, Nature Communications.

[29]  João Coelho,et al.  Quantifying the factors limiting rate performance in battery electrodes , 2018, Nature Communications.

[30]  J. Coleman,et al.  The Effect of Network Formation on the Mechanical Properties of 1D:2D Nano:Nano Composites , 2018, Chemistry of Materials.

[31]  G. Yushin,et al.  Iron Fluoride–Carbon Nanocomposite Nanofibers as Free‐Standing Cathodes for High‐Energy Lithium Batteries , 2018, Advanced Functional Materials.

[32]  Robert Vajtai,et al.  Exfoliation of a non-van der Waals material from iron ore hematite , 2018, Nature Nanotechnology.

[33]  Junle Qu,et al.  Ultrathin 2D Nonlayered Tellurium Nanosheets: Facile Liquid‐Phase Exfoliation, Characterization, and Photoresponse with High Performance and Enhanced Stability , 2018 .

[34]  Xiangyang Zhou,et al.  Enhancing the lithium storage capacity of FeF 3 cathode material by introducing C@LiF additive , 2018 .

[35]  Xianjie Liu,et al.  A Free‐Standing High‐Output Power Density Thermoelectric Device Based on Structure‐Ordered PEDOT:PSS , 2018 .

[36]  H. Abruña,et al.  Understanding Conversion-Type Electrodes for Lithium Rechargeable Batteries. , 2018, Accounts of chemical research.

[37]  Jinhui Peng,et al.  High-Temperature Electrochemical Performance of FeF3/C Nanocomposite as a Cathode Material for Lithium-Ion Batteries , 2018, Journal of Materials Engineering and Performance.

[38]  Quan-hong Yang,et al.  WS2 nanoplates embedded in graphitic carbon nanotubes with excellent electrochemical performance for lithium and sodium storage , 2018, Science China Materials.

[39]  Dianyuan Fan,et al.  2D Nonlayered Selenium Nanosheets: Facile Synthesis, Photoluminescence, and Ultrafast Photonics , 2017 .

[40]  Caihua Jiang,et al.  A truncated octahedral spinel LiMn2O4 as high-performance cathode material for ultrafast and long-life lithium-ion batteries , 2017 .

[41]  J. Coleman,et al.  Enabling Flexible Heterostructures for Li-Ion Battery Anodes Based on Nanotube and Liquid-Phase Exfoliated 2D Gallium Chalcogenide Nanosheet Colloidal Solutions. , 2017, Small.

[42]  Shu-Lei Chou,et al.  Few Atomic Layered Lithium Cathode Materials to Achieve Ultrahigh Rate Capability in Lithium‐Ion Batteries , 2017, Advanced materials.

[43]  Yong-Wei Zhang,et al.  Electrostatic‐Driven Exfoliation and Hybridization of 2D Nanomaterials , 2017, Advanced materials.

[44]  Chang Ming Li,et al.  In Situ Engineering Toward Core Regions: A Smart Way to Make Applicable FeF3@Carbon Nanoreactor Cathodes for Li-Ion Batteries. , 2017, ACS applied materials & interfaces.

[45]  Jun Lu,et al.  3D Hierarchical nano-flake/micro-flower iron fluoride with hydration water induced tunnels for secondary lithium battery cathodes , 2017 .

[46]  Thomas M. Higgins,et al.  Preparation of Liquid-exfoliated Transition Metal Dichalcogenide Nanosheets with Controlled Size and Thickness: A State of the Art Protocol. , 2016, Journal of visualized experiments : JoVE.

[47]  H. Kim,et al.  A cathode material for lithium-ion batteries based on graphitized carbon-wrapped FeF3 nanoparticles prepared by facile polymerization , 2016 .

[48]  Byoungwoo Kang,et al.  Novel and scalable solid-state synthesis of a nanocrystalline FeF3/C composite and its excellent electrochemical performance. , 2016, Chemical communications.

[49]  Jonathan N. Coleman,et al.  Production of Ni(OH)2 nanosheets by liquid phase exfoliation: from optical properties to electrochemical applications , 2016 .

[50]  Yanguang Li,et al.  Electrical, Mechanical, and Capacity Percolation Leads to High-Performance MoS2/Nanotube Composite Lithium Ion Battery Electrodes. , 2016, ACS nano.

[51]  M. Fichtner,et al.  Development of a water based process for stable conversion cathodes on the basis of FeF3 , 2016 .

[52]  Kazuhiko Matsumoto,et al.  Iron(III) fluoride synthesized by a fluorolysis method and its electrochemical properties as a positive electrode material for lithium secondary batteries , 2016 .

[53]  Xiulin Fan,et al.  In situ lithiated FeF3/C nanocomposite as high energy conversion-reaction cathode for lithium-ion batteries , 2016 .

[54]  D. N. Buckley,et al.  Comparative Electrochemical Charge Storage Properties of Bulk and Nanoscale Vanadium Oxide Electrodes , 2016, Journal of Solid State Electrochemistry.

[55]  H. Hahn,et al.  The truth about the 1st cycle Coulombic efficiency of LiNi1/3Co1/3Mn1/3O2 (NCM) cathodes. , 2016, Physical chemistry chemical physics : PCCP.

[56]  Hai Zhong,et al.  One-pot synthesis of FeF3/graphene composite for sodium secondary batteries , 2015 .

[57]  He Song,et al.  FeF3 microspheres anchored on reduced graphene oxide as a high performance cathode material for lithium ion batteries , 2015 .

[58]  Viktor Hacker,et al.  Thermal runaway of commercial 18650 Li-ion batteries with LFP and NCA cathodes – impact of state of charge and overcharge , 2015 .

[59]  H. Shu,et al.  A graphene loading heterogeneous hydrated forms iron based fluoride nanocomposite as novel and high-capacity cathode material for lithium/sodium ion batteries , 2015 .

[60]  H. Shu,et al.  Sheet-like structure FeF3/graphene composite as novel cathode material for Na ion batteries , 2015 .

[61]  K. Huth.  Transport , 2015, Canadian Medical Association Journal.

[62]  N. Pinna,et al.  A review on the application of iron(III) fluorides as positive electrodes for secondary cells , 2014, Materials for Renewable and Sustainable Energy.

[63]  Niall McEvoy,et al.  Edge and confinement effects allow in situ measurement of size and thickness of liquid-exfoliated nanosheets , 2014, Nature Communications.

[64]  J. Yamaki,et al.  Quantitative studies on thermal stability of a FeF3 cathode in methyl difluoroacetate-based electrolyte for Li-ion batteries , 2014 .

[65]  Tiffany L. Kinnibrugh,et al.  Transport, phase reactions, and hysteresis of iron fluoride and oxyfluoride conversion electrode materials for lithium batteries. , 2014, ACS applied materials & interfaces.

[66]  Liwen Yang,et al.  Hydrothermal exfoliated molybdenum disulfide nanosheets as anode material for lithium ion batteries , 2014 .

[67]  Jagjit Nanda,et al.  Electrode architectures for high capacity multivalent conversion compounds: iron (II and III) fluoride , 2014 .

[68]  Li Liu,et al.  A comparison among FeF3·3H2O, FeF3·0.33H2O and FeF3 cathode materials for lithium ion batteries: Structural, electrochemical, and mechanism studies , 2013 .

[69]  Jonathan C. Y. Chung,et al.  Large-scale fabrication of graphene-wrapped FeF3 nanocrystals as cathode materials for lithium ion batteries. , 2013, Nanoscale.

[70]  J. Coleman,et al.  Liquid Exfoliation of Layered Materials , 2013, Science.

[71]  Wei Liu,et al.  Mild and cost-effective synthesis of iron fluoride-graphene nanocomposites for high-rate Li-ion battery cathodes , 2013 .

[72]  Linsen Li,et al.  High-capacity lithium-ion battery conversion cathodes based on iron fluoride nanowires and insights into the conversion mechanism. , 2012, Nano letters.

[73]  Xin Zhao,et al.  Photothermal-assisted fabrication of iron fluoride-graphene composite paper cathodes for high-energy lithium-ion batteries. , 2012, Chemical communications.

[74]  Li Jiang,et al.  Electrochemical impedance spectroscopy investigation of the FeF3/C cathode for lithium-ion batteries , 2012 .

[75]  Li Liu,et al.  Excellent cycle performance of Co-doped FeF3/C nanocomposite cathode material for lithium-ion batteries , 2012 .

[76]  G. Wallace,et al.  Compositional effects of PEDOT-PSS/single walled carbon nanotube films on supercapacitor device performance , 2011 .

[77]  Yuto Yamakawa,et al.  Effect of heat-treatment process on FeF3 nanocomposite electrodes for rechargeable Li batteries , 2011 .

[78]  L. Gu,et al.  Carbon nanotube wiring of electrodes for high-rate lithium batteries using an imidazolium-based ionic liquid precursor as dispersant and binder: a case study on iron fluoride nanoparticles. , 2011, ACS nano.

[79]  J. Coleman,et al.  Two-Dimensional Nanosheets Produced by Liquid Exfoliation of Layered Materials , 2011, Science.

[80]  Dong-Hwa Seo,et al.  Fabrication of FeF3 Nanoflowers on CNT Branches and Their Application to High Power Lithium Rechargeable Batteries , 2010, Advanced materials.

[81]  L. Gu,et al.  Low‐Temperature Ionic‐Liquid‐Based Synthesis of Nanostructured Iron‐Based Fluoride Cathodes for Lithium Batteries. , 2010 .

[82]  L. Gu,et al.  Low‐Temperature Ionic‐Liquid‐Based Synthesis of Nanostructured Iron‐Based Fluoride Cathodes for Lithium Batteries , 2010, Advanced materials.

[83]  Zaiping Guo,et al.  Superior stability and high capacity of restacked molybdenum disulfide as anode material for lithium ion batteries. , 2010, Chemical communications.

[84]  Ting Li,et al.  Reversible Three-Electron Redox Behaviors of FeF3 Nanocrystals as High-Capacity Cathode-Active Materials for Li-Ion Batteries , 2010 .

[85]  Xianyou Wang,et al.  Effects of MoS2 doping on the electrochemical performance of FeF3 cathode materials for lithium-ion batteries , 2009 .

[86]  Richard H. Friend,et al.  Effects of Layer Thickness and Annealing of PEDOT:PSS Layers in Organic Photodetectors , 2009 .

[87]  C. Grey,et al.  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. , 2009, Journal of the American Chemical Society.

[88]  Jun-ichi Yamaki,et al.  Cathode properties of metal trifluorides in Li and Na secondary batteries , 2009 .

[89]  J. Coleman,et al.  High-yield production of graphene by liquid-phase exfoliation of graphite. , 2008, Nature nanotechnology.

[90]  Cheng-chung Lee,et al.  Process for deposition of AlF 3 thin films , 2008 .

[91]  Kaoru Dokko,et al.  Electrochemical properties of LiFePO4 prepared via hydrothermal route , 2007 .

[92]  J. Dahn,et al.  Methods to obtain excellent capacity retention in LiCoO2 cycled to 4.5 V , 2004 .

[93]  Glenn G. Amatucci,et al.  Carbon Metal Fluoride Nanocomposites High-Capacity Reversible Metal Fluoride Conversion Materials as Rechargeable Positive Electrodes for Li Batteries , 2003 .

[94]  O. Hussain,et al.  Grain size effects on the optical characteristics of pulsed‐laser deposited vanadium oxide thin films , 2003 .

[95]  P. Tyagi,et al.  Grain size dependent optical band gap of CdI2 films , 2001 .

[96]  David R. Clarke,et al.  Optical absorption edge of ZnO thin films: The effect of substrate , 1997 .

[97]  A. Barrière,et al.  Optical absorption study of iron trifluoride thin films , 1978 .

[98]  A. Barrière,et al.  Optical transitions in disordered thin films of the ionic compounds MgF(2) and AIF(3) as a function of their conditions of preparation. , 1977, Applied optics.