Investigation of the sodium storage mechanism of iron fluoride hydrate cathodes using X-ray absorption spectroscopy and mossbauer spectroscopy

Elucidation of a reaction mechanism is the most critical aspect for designing electrodes for highperformance secondary batteries.Herein,we investigate the sodium insertion/extraction into an iron fluoride hydrate(FeF_(3)·0.5H_(2)O)electrode for sodium-ion batteries(SIBs).The electrode material is prepared by employing an ionic liquid 1-butyl-3-methylimidazolium-tetrafluoroborate,which serves as a reaction medium and precursor for F^(-)ions.The crystal structure of FeF_(3)·0.5H_(2)O is observed as pyrochlore type with large open 3-D tunnels and a unit cell volume of 1129A^(3).The morphology of FeF_(3)·0.5H_(2)O is spherical shape with a mesoporous structure.The microstructure analysis reveals primary particle size of around 10 nm.The FeF_(3)·0.5H_(2)O cathode exhibits stable discharge capacities of 158,210,and 284 mA h g^(-1) in three different potential ranges of 1.5-4.5,1.2-4.5,and 1.0-4.5 V,respectively at 0.05 C rate.The specific capacities remained stable in over 50 cycles in all three potential ranges,while the rate capability was best in the potential range of 1.5-4.5 V.The electrochemical sodium storage mechanism is studied using X-ray absorption spectroscopy,indicating higher conversion at a more discharged state.Ex-situ M?ssbauer spectroscopy strengthens the results for reversible reduction/oxidation of Fe.These results will be favorable to establish high-performance cathode materials with selective voltage window for SIBs.

Designing mesostructured iron (Ⅱ) fluorides with a stable in situ polymer electrolyte interface for high-energy-density lithium-ion batteries

As high-energy cathode materials,conversion-type metal fluorides provide a prospective pathway for developing next-generation lithium-ion batteries.However,they suffer from severe performance decay owing to continuous structural destruction and active material dissolution upon cycling,which worsen at elevated temperatures.Here,we design a novel FeF2 cathode with in situ polymerized solid-state electrolyte systems to enhance the cycling ability of metal fluorides at 60 C.Novel FeF2 with a mesoporous structure(meso-FeF2)improves Liþdiffusion and relieves the volume change that typically occurs during the alternating conversion reactions.The structural stability of the meso-FeF2 cathode is strengthened by an in situ polymerized solid-state electrolyte,which prevents the pulverization and ion dissolution that are inevitable for conventional liquid electrolytes.Under the double action of this in situ polymerized solid-state electrolyte and the meso-FeF2's mesoporous structure,the active material maintains an intact SEI layer and part of the mesoporous structure after long charge–discharge cycling,showing excellent cycling stability at high temperatures.

Structure, Thermal Behavior and Characterization of a New Hybrid Iron Fluoride FeF4（2,2′-bipyridine）（H2O）2

New crystal of FeF4（2,2′-bipyridine）（H2O）2 was prepared by hydrothermal synthesis. Crystalline structure determination is performed from single crystal X-ray diffraction data. The unit cell is monoclinic space group P21/n, with cell parameters a=0.9046（5） nm, b=0.7502（5） nm, c=1.9539（5） nm,β=93.307（5）°, V=1.3238（12） nm^3 and Z=4. The structure of FeF4（2,2＇-bipyridine）（H2O）2 is built up from FeF4N2 octahedra coordinated by two nitrogen atoms of the 2,2＇-bipyridine molecules, and four fluorine atoms as well as uncoordinated H2O molecules. Thermal analysis of the title compound showed that the decomposition introduced four steps. IR spectra confirmed the presence of 2,2＇-bipyridine molecules. The optical absorption was measured at the corresponding 2max using UV-Vis diffuse reflectance spectrum.

Carbon coating of air-sensitive insulating transition metal fluorides:An example study on α-Li3FeF6 high-performance cathode for lithium ion batteries

Li_(3)FeF_(6)has been the focus of research of fluorine-based cathode materials for lithium-ion batteries.Because of the low electronic conductivity of Li3 FeF6,the decrease of particle size,by an energyconsuming long-time ball milling process with carbon,is necessary to achieve a high electrochemical performance.The most successful method to enhance electrochemical activity,carbon coating,seemed to be impracticable,so far,for sensitive fluorides like Li3 FeF6.In this work,carbon coating on Li3 FeF6 particles has been successfully achieved for the first time,while avoiding both extended hydrolysis and Fe(Ⅲ)-Fe(Ⅱ)reduction.The heat treatment and atmosphere,yielding the maximal transformation of organic carbon to both graphitised and disordered carbon,has been determined.Carbon coating,with a thickness of approximately 2.5 nm,has been achieved by controlled thermal decomposition of glucose,under air,at 300℃.Raman and X-ray photoelectron spectroscopy(XPS)experiments have proved the existence of carbon and Fe2O3 on the surface of Li3FeF6 nanoparticles.XPS spectroscopy indicates the presence of organic residues from glucose decomposition.Attempts to further reduce the orga nic carbon content results in a decrease of the amorphous carbon coating layer.Optimised carbon-coated Li3 FeF6 nanoparticles deliver 122 mA h g^(-1)(85%of theoretical capacity)significantly higher than that of a noncoated sample(58 mA h g^(-1)).Even more,a significant beneficial effect of carbon coating on both capacity retention and coulombic efficiency is observed.

Engineering sphere-like porous FeF3@C cathode with rational interfacial designing towards high-power batteries

Due to the high theoretical capacity and energy density,conversion-type metal fluorides have captured plenty of attentions but still suffer from the inferior kinetic behaviors and serious capacity fading.For addressing the issues above,the strategies of surface/interface engineering are utilized for the preparation of sphere-like porous FeF3@C materials,where the as-resulted sample displays the uniform particle size(~150 nm in radii)and the ultrathin carbon layers(thickness of~10 nm).Significantly,benefitting from the rich oxygen of precursor,the interfacial chemical bonds Fe-O-C are successfully constructed between carbon matrix and FeF3 materials,accompanying by the enhancements of ions/electrons(e-)conductivity and stability.When used as Li-storage cathodes,the initial lithium-ions storage capacity could reach up to~400mAh·g^(-1) at 0.1 A·g^(-1).Even at 1.0 A·g^(-1),the capacity could be still remained at about 210 mAh·g^(-1),with the retention of 85%after 400 cycles.Assisted by the detailed kinetic behaviors,the considerable electrochemical properties come from the enhanced diffusion-controlled contributions,whilst the segregation of Fe with LiF is effectively alleviated by unique architecture.Moreover,during cycling,solid electrolyte interface film is reversibly formed/decomposed.Thus,this work is expected to offer rational exterior/interfacial designing strategies for metalbased samples.