Mechanical synthesis and structural properties of the fast fluoride-ion conductor PbSnF4

Fujisaki, Fumika; Mori, Kazuhiro; Yonemura, Masao; Ishikawa, Yoshihisa; Kamiyama, Takashi; Otomo, Toshiya; Matsubara, Eiichiro; Fukunaga, Toshiharu

doi:10.1016/j.jssc.2017.06.007

Cited by 36 publications

(57 citation statements)

References 33 publications

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“…Note that the conductivity for the β−PbSnF4 sample (~ 2.2× 10 -3 Scm -1 ) is comparable to that reported previously for β−PbSnF4 prepared without annealing (~1.6 × 10 -3 Scm -1 ) 21 and β−PbSnF4 prepared with annealing at 200 °C (~1.6 × 10 -3 Scm -1 ). 19 The conductivity values of the samples with x = 1.15~1.25 are higher than that of the β−PbSnF4 sample. The sample prepared by cold pressing of the PbxSn2-xF4 powder showed the ionic conductivity as high as ~ 3.5× 10 -3 Scm -1 at x = 1.21.…”

Section: Resultsmentioning

confidence: 85%

“…It is apparent that facile transportation of Fions is supported by its unique Sn-Pb layer structure with the "gap" between the Pb layer and the Sn layer that offers a conduction path. The fast Fmotion should reduce the 19 F-207 Pb dipolar interactions and it was in fact observed that 19 F dipolar decoupling brings no apparent line narrowing for the 207 Pb MAS spectra (not shown). As the strength of the 19 F-207 Pb dipolar interactions at the three different Pb sites is a good measure of the mobility of the Fions in the conduction path, that is, through the double Pb layer and through the triple Pb layers, the 19 F to 207 Pb CP experiments were pursued; the CP transfer rate is sensitive to the strength of the 19 F-207 Pb dipolar interaction.…”

Section: Resultsmentioning

confidence: 93%

“…It is suggested that the β + -form consists of two alternating layers; one layer resembles to the double layer of the β-form (the region designated by a two-way arrow in Figure 3 Figure 4 compares 19 F, 119 Sn, and 207 Pb MAS NMR spectra of the two samples (β and β + ). All spectra were taken by using the single-pulse sequence without the Hahn echo for 19 F, and with the Hahn echo for 119 Sn and 207 Pb. The 207 Pb spectrum of the β + sample taken by using 19 F to 207 Pb CP is also given, which will be discussed afterward.…”

Section: Resultsmentioning

confidence: 99%

“…All spectra were taken by using the single-pulse sequence without the Hahn echo for 19 F, and with the Hahn echo for 119 Sn and 207 Pb. The 207 Pb spectrum of the β + sample taken by using 19 F to 207 Pb CP is also given, which will be discussed afterward.…”

Section: Resultsmentioning

confidence: 99%

“…The NMR measurements were made using a JEOL ECA600 NMR spectrometer with a triple-tuned MAS probe (Agilent Technologies Inc.) for a 1.6 mm rotor at 14 T. The resonance frequencies for 19 The MAS NMR spectra were observed by using a single-pulse method or a cross-polarization (CP) method. Except for 19 F experiments, the Hahn echo was used with the echo-delay time being 1/νR -pw/2, where νR is the MAS spinning frequency and pw is the π pulse length. The CP experiment between 19 F and 207 Pb spins was made by the conventional constant-amplitude CP pulse sequence.…”

Section: Nmr Measurementmentioning

confidence: 99%

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High Anionic Conductive Form of Pb_xSn_2–xF₄

et al. 2019

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High anionic conductivity of ~ 3.5 × 10-3 Scm-1 at room temperature is achieved for PbxSn2-xF4 (x = 1.21) obtained by annealing a mechanically-milled PbF2/SnF2 mixture at 400 °C. The observed synchrotron X-ray diffraction patterns indicate formation of a new tetragonal phase at x = 1.1 ~ 1.3. The Rietveld analysis of the neutron diffraction patterns leads to a unique structure consisting of two alternating layers; a double Pb layer and a triple layer, each flanked by a single Sn layer. As the Rietveld analysis does not fully converge, the authors further apply high-resolution solid-state NMR (19 F, 119 Sn, and 207 Pb) to confirm the structure. Further the 19 F-207 Pb cross-polarization experiment shows that most of Fions, except for those lie between the double Pb layers, contribute to its high ionic conductivity. The high conductivity is also attributed to structural flexibility of the triple Pb layers, indicated by temperature dependent 207 Pb NMR spectra.

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Section: Resultsmentioning

confidence: 85%

Section: Resultsmentioning

confidence: 93%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Nmr Measurementmentioning

confidence: 99%

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High Anionic Conductive Form of Pb_xSn_2–xF₄

et al. 2019

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A Fluoride‐Ion‐Conducting Solid Electrolyte with Both High Conductivity and Excellent Electrochemical Stability

Wang

Hao

Duan

et al. 2021

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Solid‐state fluoride‐ion batteries (FIBs) circumvent multiple formidable bottlenecks of lithium‐ion batteries, but their overall performance remains inferior due to the absence of appropriate solid electrolytes. Presently the conductivity of most solid electrolytes for FIBs is too low to enable room‐temperature cycling, while the few sufficiently conductive ones only allow for very low discharge voltages because of the narrow electrochemical stability window (ESW). Here, high room‐temperature conductivity and a decent ESW are simultaneously achieved by designing a solid electrolyte CsPb0.9K0.1F2.9. Its room‐temperature conductivity is 1.23 × 10−3 S cm−1, comparable to the most conductive system reported so far (PbSnF4, 5.44 × 10−4–1.6 × 10−3 S cm−1), but the ESW is several times broader. With these appealing characteristics simultaneously achieved in the solid electrolyte, a cell with much higher voltages than other room‐temperature‐operable solid‐state FIBs in literature is successfully constructed, and stably cycled at 25 °C for 4581 h without considerable capacity fade.

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Pressure Tuning and Sn Particle Size Optimization for Enhanced Performance in PbSnF₄‐Based All‐Solid‐State Fluoride Ion Batteries

Wei,

Liu,

Xiao

et al. 2024

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All‐solid‐state fluoride ion batteries (ASSFIBs) show remarkable potential as energy storage devices due to their low cost, superior safety, and high energy density. However, the poor ionic conductivity of F− conductor, large volume expansion, and the lack of a suitable anode inhibit their development. In this work, PbSnF4 solid electrolytes in different phases (β‐ and γ‐PbSnF4) are successfully synthesized and characterized. The ASSFIBs composed of β‐PbSnF4 electrolytes, a BiF3 cathode, and micrometer/nanometer size (µ‐/n‐) Sn anodes, exhibit substantial capacities. Compared to the μ‐Sn anode, the n‐Sn anode with nanostructure exhibits superior battery performance in the BiF3/β‐PbSnF4/Sn battery. The optimized battery delivers a high initial discharge capacity of 181.3 mAh g−1 at 8 mA g−1 and can be reversibly cycled at 40 mA g−1 with a high discharge capacity of over 100.0 mAh g−1 after 120 cycles at room temperature. Additionally, it displays high discharge capacities over 90.0 mAh g−1 with excellent cyclability over 100 cycles under ‐20 °C. Detailed characterization has confirmed that reducing Sn particle size and boosting external pressure are crucial for achieving good defluorination/fluorination behaviors in the Sn anode. These findings pave the way to designing ASSFIBs with high capacities and superior cyclability under different operating temperatures.

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Mechanical synthesis and structural properties of the fast fluoride-ion conductor PbSnF4

Cited by 36 publications

References 33 publications

High Anionic Conductive Form of Pb_xSn_2–xF₄

High Anionic Conductive Form of Pb_xSn_2–xF₄

A Fluoride‐Ion‐Conducting Solid Electrolyte with Both High Conductivity and Excellent Electrochemical Stability

Pressure Tuning and Sn Particle Size Optimization for Enhanced Performance in PbSnF₄‐Based All‐Solid‐State Fluoride Ion Batteries

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Mechanical synthesis and structural properties of the fast fluoride-ion conductor PbSnF4

Cited by 36 publications

References 33 publications

High Anionic Conductive Form of PbxSn2–xF4

High Anionic Conductive Form of PbxSn2–xF4

A Fluoride‐Ion‐Conducting Solid Electrolyte with Both High Conductivity and Excellent Electrochemical Stability

Pressure Tuning and Sn Particle Size Optimization for Enhanced Performance in PbSnF4‐Based All‐Solid‐State Fluoride Ion Batteries

Contact Info

Product

Resources

About

High Anionic Conductive Form of Pb_xSn_2–xF₄

High Anionic Conductive Form of Pb_xSn_2–xF₄

Pressure Tuning and Sn Particle Size Optimization for Enhanced Performance in PbSnF₄‐Based All‐Solid‐State Fluoride Ion Batteries