Influence of microstructures on conductivity in Tysonite-type fluoride ion conductors

Motohashi, Kota; Nakamura, Takashi; Kimura, Yuta; Uchimoto, Yoshiharu; Amezawa, Koji

doi:10.1016/j.ssi.2019.05.023

Cited by 32 publications

(23 citation statements)

References 30 publications

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“…In our previous study, 14,27,28 we demonstrated that the 3dtransition-metal cathode (Cu, Co, and Ni) and the selfgenerated La/LaF 3 anode in thin-film all-solid-state FIBs show clear charge−discharge behavior. The combinations of Cu, Co, and Ni cathodes and representative anodes (La/LaF 3 , Ce/ CeF 2 , Pb/PbF 2 , etc.)…”

Section: Introductionmentioning

confidence: 91%

Rate-Determining Process at Electrode/Electrolyte Interfaces for All-Solid-State Fluoride-Ion Batteries

Zhang

Nakano

Yamamoto

et al. 2021

ACS Appl. Mater. Interfaces

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Developing high-performance solid electrolytes that are operable at room temperature is one of the toughest challenges related to all-solid-state fluoride-ion batteries (FIBs). In this study, tetragonal β-Pb 0.78 Sn 1.22 F 4 , a promising solid electrolyte material for mild-temperature applications, was modified through annealing under various atmospheres using thin-film models. The annealed samples exhibited preferential growth and enhanced ionic conductivities. The ratedetermining factor for electrode/electrolyte interface reactions in all-solid-state FIBs was also investigated by comparing β-Pb 0.78 Sn 1.22 F 4 with representative fluoride-ionand lithium-ion-conductive materials, namely, LaF 3 , CeF 3 , and Li 7 La 3 Zr 2 O 12 . The overall rate constant of the interfacial reaction, k 0 , which included both mass and charge transfers, was determined using chronoamperometric measurements and Allen-Hickling simulations. Arrhenius-type correlations between k 0 and temperature indicated that activation energies calculated from k 0 and ionic conductivities (σ ion ) were highly consistent. The results indicated that the mass transfer (electrolyte-side fluoride-ion conduction) should be the rate-determining process at the electrode/electrolyte interface. β-Pb 0.78 Sn 1.22 F 4 , with a large σ ion value, had a larger k 0 value than Li 7 La 3 Zr 2 O 12 . Therefore, it is hoped that the development of high-conductivity solid electrolytes can lead to all-solid-state FIBs with superior rate capabilities similar to those of all-solid-state Li-ion batteries.

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Section: Introductionmentioning

confidence: 91%

Rate-Determining Process at Electrode/Electrolyte Interfaces for All-Solid-State Fluoride-Ion Batteries

Zhang

Nakano

Yamamoto

et al. 2021

ACS Appl. Mater. Interfaces

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“…Further, LBF prepared by high energy ball milling method can be improved via sintering at high temperature. 8,39,40 The ionic conductivities of compacted, unsintered La0.90Ba0.10F2.90 (1.6 × 10 4 S•cm 1 at 160 °C) can be significantly improved by a further sintering step at 800 °C for 2 h to 10 5 S•cm 1 at room temperature (Figure 4b). This observation within tysonite-type LBF fluoride ion conductors is explained by the differences in the grain boundary structure, which can result in a partial blocking of the migration pathways, and has been observed for various anion conducting compounds.…”

Section: Ionic Conductivity Of Rare-earth Fluorides With Tysonite-typmentioning

confidence: 99%

Fluoride ion batteries – past, present, and future

et al. 2021

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“…On the other hand, the tysonite-type La 1- x Ba x F 3- x and Sm 1- x Ca x F 3- x and the fluorite-type Sn 1- x K x F 2- x and Ba 1- x La x F 2+ x are the materials based on the latter one 11 – 14 . Although various fluoride ion conductors are previously reported 15 , 16 , further material explorations for sufficiently high fluoride ion conductivity are required to realize ASSFIBs.…”

Section: Introductionmentioning

confidence: 99%

Fast fluoride ion conduction of NH4(Mg1-xLix)F3-x and (NH4)2(Mg1-xLix)F4-x assisted by molecular cations

Motohashi

Matsukawa

Nakamura

et al. 2022

Sci Rep

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Aiming development of the fast anion conductors, we proposed a new material design using flexible molecular cation as a host cation, and demonstrated it with fluoride ion conduction in NH4MgF3 and (NH4)2MgF4 based materials. Dominant fluoride ion conduction with relatively high conductivities of 4.8 × 10–5 S cm−1 and 8.4 × 10–6 S cm−1 were achieved at 323 K in (NH4)2(Mg0.85Li0.15)F3.85 and NH4(Mg0.9Li0.1)F2.9, respectively. It is implied that the molecular cation in the host lattice can assist the anion conduction. Our findings suggest molecular cation-containing compounds can be attractive material groups for fast anion conductors.

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Influence of microstructures on conductivity in Tysonite-type fluoride ion conductors

Cited by 32 publications

References 30 publications

Rate-Determining Process at Electrode/Electrolyte Interfaces for All-Solid-State Fluoride-Ion Batteries

Rate-Determining Process at Electrode/Electrolyte Interfaces for All-Solid-State Fluoride-Ion Batteries

Fluoride ion batteries – past, present, and future

Fast fluoride ion conduction of NH4(Mg1-xLix)F3-x and (NH4)2(Mg1-xLix)F4-x assisted by molecular cations

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