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

Datong Zhang, Hiroyuki Nakano, Kentaro Yamamoto, Kenta Tanaka, Tatsuma Yahara, Kazuyuki Imai, Takuya Mori, Hidenori Miki, Shinji Nakanishi, Hideki Iba, Toshiki Watanabe, Tomoki Uchiyama, Koji Amezawa, Yoshiharu Uchimoto

Research output: Contribution to journalArticlepeer-review

Abstract

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-Pb0.78Sn1.22F4, 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 rate-determining factor for electrode/electrolyte interface reactions in all-solid-state FIBs was also investigated by comparing β-Pb0.78Sn1.22F4 with representative fluoride-ion- and lithium-ion-conductive materials, namely, LaF3, CeF3, and Li7La3Zr2O12. The overall rate constant of the interfacial reaction, k0, which included both mass and charge transfers, was determined using chronoamperometric measurements and Allen-Hickling simulations. Arrhenius-type correlations between k0 and temperature indicated that activation energies calculated from k0 and ionic conductivities (σion) 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-Pb0.78Sn1.22F4, with a large σion value, had a larger k0 value than Li7La3Zr2O12. 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.

Original languageEnglish
Pages (from-to)30198-30204
Number of pages7
JournalACS Applied Materials and Interfaces
Volume13
Issue number25
DOIs
Publication statusPublished - 2021 Jun 30

Keywords

  • all-solid-state battery
  • electrolyte
  • interfaces
  • kinetics
  • rate-determining steps

ASJC Scopus subject areas

  • Materials Science(all)

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