Intercalation Reaction Mechanism of Fluoride-Ions in (Ca, Sr)FeO2 Cathodes with Infinite Layer Structure for All-Solid-State Fluoride-Ion Batteries
Authors: Yamamoto Kentaro , Wang Yanchang , Kiuchi Hisao , Matsunaga Toshiyuki , Watanabe Toshiki , Miki Hidenori , Iba Hideki , Maeda Kazuhiko , Harada Yoshihisa , Kageyama Hiroshi , Uchimoto Yoshiharu 
Published: February 2024

Fluoride ion batteries, which use fluoride ions as carriers, are attracting attention as the next generation of storage batteries because of their theoretical high energy density. Conventional research has focused on metal/metal fluorides such as Cu/CuF2 as cathode materials.[1] However, these cathodes have disadvantages of the power density and cyclability due to the rapid decrease in electronic conductivity and large volume change during fluorination and defluorination. To solve these problems, cathode materials that utilize topotactic fluoride ion intercalation reactions, similar to electrode materials applied in lithium-ion secondary batteries, are being developed[2]. However, these materials have the disadvantage of relatively small capacity, compared to metal/metal fluorides.In this study, we focused on SrFeO2and Ca-doped SrFeO2 cathodes with infinite layer structure as new high-capacity intercalation cathodes, and evaluated its electrochemical properties and clarified the charge compensation mechanism.

Ca1-xSrxFeO2 (x = 0, 0.2, 0.4, 0.6, 0.8, 1.0) was synthesized by a low-temperature reduction method using CaH2. Ca1-xSrxFeO2/La0.9Ba0.1F2.9/vapor grown carbon fiber (VGCF) was used as the composite cathode, La0.9Ba0.1F2.9 as the electrolyte and Pb/PbF2/ La0.9Ba0.1F2.9/VGCF as the composite anode to construct the electrochemical cell of the piezoelectric material. Charge-discharge measurements were carried out in the cut-off voltage range of -1.5 to 3.0 V at 140°C. X-ray absorption spectroscopy (XAS) measurements of Fe K-edge, O K-edge, and F K-edge and resonant inelastic X-ray scattering (RIXS) measurements of O K-edge were performed on the samples after charging and discharging.

All the Ca1-xSrxFeO2 (x = 0, 0.2, 0.4, 0.6, 0.8, 1.0) cathode showed voltage plateaus around -0.5 V and 1.5 V during charging, and the maximum discharge capacity (580 mAh g-1) was obtained when x = 0.8, and the cathodes could be repeatedly charged and discharged. XAS of the Fe K-edge revealed that Fe compensated for the charge in the flat potential region around -0.5 V. XAS and RIXS measurements of the O K-edge revealed that the charge compensation was carried out by the formation of O2 molecules (oxidation of oxide ions), as which is observed in lithium-excess metal oxide on charge process[4], in the voltage plateau around 1.5 V. Using inexpensive Ca and Fe, we succeeded in developing an intercalation cathode material that significantly exceeds the capacity of conventional lithium-ion battery cathodes.

References:

[1] D. Zhang, K. Yamamoto, Y. Uchimoto et al., J. Mater. Chem. A, 2021, 9, 406–412.

[2] Y. Wang, K. Yamamoto, Y. Uchimoto, et al., Chem. Mater., 2022, 34, 609–616.

[3] C. Tassel, T. H. Kageyama, et al., J. Am. Chem. Soc., 2008, 130, 3764–3765.

[4] R. A. House, P. G. Bruce, et al., Nat. Energy 2020, 5, 777–785.

Acknowledgement:

This research was financially supported by Grant-in-Aid for Scientific Research (B) (JSPS KAKENHI Grant Number JP21H02048).