Topotactic Fluorine Insertion into the Channels of FeSb<sub>2</sub>O<sub>4</sub>-Related Materials

Laune, Benjamin P. de; Rees, Gregory J.; Marco, José F.; Hah, Hien-Yoong; Johnson, C. E.; Johnson, Jacqueline A.; Berry, Frank J.; Hanna, John V.; Greaves, C.

doi:10.1021/acs.inorgchem.7b01613

Cited by 12 publications

(27 citation statements)

References 21 publications

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“…In this article, we investigate their suitability for electrochemical applications within all‐solid‐state fluoride‐ion batteries. The inclusion of 0.5 F per formula unit corresponds to the specific charging capacity of roughly 36–39 mA h g −1 . We show that this class of material is found to be the second suitable host material for the fully reversible intercalation/deintercalation of fluoride ions.…”

Section: Introductionsupporting

confidence: 81%

“…Furthermore, we note that the potential for the fluorination of the schafarzikite compounds, which only involves the Fe 2+ /Fe 3+ redox couple, is higher than Mn 3+ /Mn 4+ and Co 2+ /Co 3+ in LaSrMnO 4 and La 2 CoO 4 , respectively (ca. 1.2 V for LaSrMnO 4 and 0.9 V for La 2 CoO 4 against a composite of Pb+PbF 2 at the same condition), and this would not be expected intuitively from the electrochemical series .…”

Section: Resultsmentioning

confidence: 96%

“…Greaves and co‐workers reported a capacity of approximately 0.5 fluoride ions per formula unit Mg 0.5 Fe 0.5 Sb 2 O 4 and Co 0.5 Fe 0.5 Sb 2 O 4 via chemical fluorination, which would correspond to capacities of 36–39 mAh g −1 for the charging/electrochemical oxidation reaction corresponding to [Eq. ]:

true MSb_{2} normalO_{4} + 0.5 normalF^{-} \to MSb_{2} normalO_{4} normalF_{0.5} + 0.5 normale^{-}

…”

Section: Resultsmentioning

confidence: 97%

“…Recent studies have shown that it is possible to fluorinate variants of this material (see Figure ), which contain Fe 2+ on the M site, by using topochemical reactions . The proposed mechanism for fluorination is based on two key principles . Firstly, the phase must possess Fe 2+ to act as the redox active center whilst the degree of oxidation is limited to the amount of Fe 2+ to be oxidized to Fe 3+ .…”

Section: Introductionmentioning

confidence: 96%

“…The structure can be understood as being built up of chains of edge‐linked MO 6 octahedra running along the [0 0 1] direction; the chains are connected through trigonal pyramidal SbO 3 units. Recent studies have shown that it is possible to fluorinate variants of this material (see Figure ), which contain Fe 2+ on the M site, by using topochemical reactions . The proposed mechanism for fluorination is based on two key principles .…”

Section: Introductionmentioning

confidence: 97%

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Reversible Electrochemical Intercalation and Deintercalation of Fluoride Ions into Host Lattices with Schafarzikite‐Type Structure

2018

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Herein, we report the successful electrochemical fluorination and defluorination of schafarzikite‐type compounds with the composition Fe0.5 m 0.5Sb2O4 (M=Mg or Co). We show that electrochemical methods can present a more controllable and less environmentally damaging route for fluorinating compounds in contrast to traditional methods that involve heating samples in F2‐rich atmospheres. The reactivity of the host lattices with fluoride during electrochemical fluorination makes this material an interesting candidate for fluoride‐ion battery applications. However, deleterious side reactions with the conductive carbon matrix during fluorination suggests to the contrary. Regardless of the side reactions, the schafarzikite structure was found to be an alternative reversible host lattice for fluoride incorporation and removal in addition to the previously reported Ruddlesden–Popper‐type compounds.

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Section: Introductionsupporting

confidence: 81%

Section: Resultsmentioning

confidence: 96%

true MSb_{2} normalO_{4} + 0.5 normalF^{-} \to MSb_{2} normalO_{4} normalF_{0.5} + 0.5 normale^{-}

…”

Section: Resultsmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 96%

Section: Introductionmentioning

confidence: 97%

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Reversible Electrochemical Intercalation and Deintercalation of Fluoride Ions into Host Lattices with Schafarzikite‐Type Structure

2018

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Reversible and Fast (De)fluorination of High‐Capacity Cu₂O Cathode: One Step Toward Practically Applicable All‐Solid‐State Fluoride‐Ion Battery

Zhang

Yamamoto

Wang

et al. 2021

Advanced Energy Materials

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and sustainable society; however, LIBs are facing bottlenecks in terms of energy/ power density and safety. [1,2] In recent decades, many new concepts for batteries have been proposed as potential alternatives for LIBs, such as battery systems that employ Na + , K + , Mg 2+ , Zn 2+ , Ca 2+ , Al 3+ , F − , or Cl − as charge carriers, which have significantly expanded the strategies for developing next-generation batteries with high energy and power densities. [3,4] All-solid-state fluoride-ion batteries (FIBs) have received widespread attention because of the high electronegativity of fluorine. This leads to extraordinary anodic electrochemical stability, resulting in superior reliability for solid-state utilization. In early studies, including our recent ones, simple metal/metal fluoride (M/MF x ) systems were first used as electrode materials with high theoretical capacities. [3,[5][6][7][8][9] Using M/MF x systems, it is theoretically feasible to fabricate batteries with high energy densities because the working potential can exceed 3 V if suitable cathode-anode combinations are selected. However, closepacked metal atoms (e.g., Cu, Co, Ni, and Bi) provide no diffusion path for F anions in conversion-type M/MF x systems; as a result, M/MF x systems inevitably suffer from thorough atomic rearrangements and undesired volumetric changes upon All-solid-state fluoride-ion batteries (FIBs) are regarded as promising energy storage devices; however, currently proposed cathodes fail to meet the requirements for practical applications in terms of high energy density and high rate capability. Herein, the first use of stable and low-cost cuprous oxide (Cu 2 O) as a cathode material for all-solid-state FIBs with reversible and fast (de)fluorination behavior is reported. A phase-transition reaction mechanism involving Cu + /Cu 2+ redox for charge compensation is confirmed, using the combination of electrochemical methods and X-ray absorption spectroscopy. The first discharge capacity is approximately 220 mAh g −1 , and fast capacity fading is observed in the first five cycles, which is ascribed to partial structural amorphization. Compared with those of simple metal/metal fluoride systems, the material shows a superior rate capability, with a first discharge capacity of 110 mAh g −1 at 1 C. The rate-determining step and probable structural evolutions are investigated as well. It is believed that the comprehensive investigations of Cu 2 O as a cathode material described in this work can lead to an improved understanding of all-solid-state FIBs.

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57Fe Mössbauer spectra from fluorinated phases of Fe0.50M0.50(M = Co,Mg)Sb2O4

et al. 2019

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Fluorinated phases formed by reaction of Fe 0.5 Co 0.5 Sb 2 O 4 and Fe 0.5 Mg 0.5 Sb 2 O 4 with gaseous fluorine have been examined by 57 Fe Mössbauer spectroscopy between 298 and 5 K. The degree of oxidation of Fe 2+ to Fe 3 + has been used to quantify the amount of fluorine incorporated within the channels of the schafarzikite-related structure and enable the evaluation of the compositions as Fe 0.5 Co 0.5 Sb 2 O 4 F 0.41 and Fe 0.5 Mg 0.5 Sb 2 O 4 F 0.31. The multiplicity of components observed in the spectra recorded in the paramagnetic regime can be related to the number of near neighbour fluoride ions which lie in the channels at the same value of the crystal zcoordinate as the iron ions. Comparison of the magnetically ordered spectra recorded at lower temperatures from Co 0.5 Fe 0.5 Sb 2 O 4 F 0.41 with those recorded previously from FeSb 2 O 4 indicates that the insertion of fluoride ions into the channels of the structure does not affect the angle between the EFG and magnetic hyperfine field.

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Topotactic Fluorine Insertion into the Channels of FeSb₂O₄-Related Materials

Cited by 12 publications

References 21 publications

Reversible Electrochemical Intercalation and Deintercalation of Fluoride Ions into Host Lattices with Schafarzikite‐Type Structure

Reversible Electrochemical Intercalation and Deintercalation of Fluoride Ions into Host Lattices with Schafarzikite‐Type Structure

Reversible and Fast (De)fluorination of High‐Capacity Cu₂O Cathode: One Step Toward Practically Applicable All‐Solid‐State Fluoride‐Ion Battery

57Fe Mössbauer spectra from fluorinated phases of Fe0.50M0.50(M = Co,Mg)Sb2O4

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Topotactic Fluorine Insertion into the Channels of FeSb2O4-Related Materials

Cited by 12 publications

References 21 publications

Reversible Electrochemical Intercalation and Deintercalation of Fluoride Ions into Host Lattices with Schafarzikite‐Type Structure

Reversible Electrochemical Intercalation and Deintercalation of Fluoride Ions into Host Lattices with Schafarzikite‐Type Structure

Reversible and Fast (De)fluorination of High‐Capacity Cu2O Cathode: One Step Toward Practically Applicable All‐Solid‐State Fluoride‐Ion Battery

57Fe Mössbauer spectra from fluorinated phases of Fe0.50M0.50(M = Co,Mg)Sb2O4

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Product

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Topotactic Fluorine Insertion into the Channels of FeSb₂O₄-Related Materials

Reversible and Fast (De)fluorination of High‐Capacity Cu₂O Cathode: One Step Toward Practically Applicable All‐Solid‐State Fluoride‐Ion Battery