Boosting the electrocatalytic performance of double perovskite air electrodes via Rb-doping for oxygen reduction and hydrogen production in reversible protonic ceramic electrochemical cells

doi:10.1016/S1872-2067(25)64786-3

Abstract

Abstract:

The slow oxygen reaction kinetics of air electrodes impair the performance of reversible protonic ceramic electrochemical cells (R-PCECs); hence, it is imperative to design novel air electrodes featuring excellent catalytic activity and endurance. Here, we report an Rb-doped double perovskite PrBa_0.8Ca_0.1Rb_0.1Co₂O₅₊_δ (denoted as PBCR_0.1C) as an air electrode for R-PCECs, displaying a low polarization resistance of 0.044 Ω cm² at 700 °C and excellent stability during exposure to humid air (3 vol% H₂O). The high performance is attributed to the high electrical conductivity, high concentration of oxygen vacancies, and fast surface exchange, as verified by the analyses of X-ray photoelectron spectroscopy, thermogravimetric testing, and conductivity tests. The R-PCECs with the PBCR_0.1C air electrode demonstrate an encouraging performance at 700 °C: a peak power density of 2.32 W cm^-2 in a fuel cell (FC) mode and an electrolysis current density of -3.55 A cm^-2 at 1.3 V in an electrolysis (EL) mode. At 30 vol% steam concentration, a Faraday efficiency of 87.80% and a corresponding H₂ production rate of 3.05 mL min^-1 cm^-2 at a current density of -0.5 A cm^-2 at 650 °C. Additionally, the durability of the cell in the FC mode (120 h), EL mode (120 h), and cycling FC/EL mode (100 h) at 650 °C suggests the great potential of PBCR_0.1C as the highly reactive and robust air electrodes of R-PCECs.

Key words: Air electrode, Stability, Rubidium-doping, Reversible protonic ceramic, electrochemical cells, Oxygen reduction/evolution reaction

Chuqian Jian, Yixuan Huang, Hui Gao, Jiaojiao Xia, Wenjie Gong, Xirui Zhang, Xiaofeng Chen, Jiang Liu, Ying Liu, Yu Chen. Boosting the electrocatalytic performance of double perovskite air electrodes via Rb-doping for oxygen reduction and hydrogen production in reversible protonic ceramic electrochemical cells[J]. Chinese Journal of Catalysis, 2025, 78: 313-323.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64786-3

https://www.cjcatal.com/EN/Y2025/V78/I11/313

Figures/Tables 5

Fig. 1. Phase structure of PBCR0.1C powder. (a) Refined XRD profiles of PBCR0.1C sample after being fired in air at 950 °C for 2 h. (b) XRD profiles of PBCC and PBCR0.1C powders. (c) Detailed XRD patterns of PBCR0.1C and PBCC in 2θ of 32°-34°, corresponding to the dashed box in (b). TEM (d) and HR-TEM (e) images of the PBCR0.1C sample and corresponding FFT pattern. (f) A linear scanning pattern within the red frame in (e). (g) STEM image and corresponding EDS mapping results of Pr, Ba, Ca, Rb, Co, and O on PBCR0.1C.

Fig. 2. Symmetrical cell performance of the PBCR0.1C air electrode. (a) The EIS curves PBCR0.1C symmetrical cells from 500 to 700 °C. (b) Polarization resistance of PBCR0.1C and PBCC air electrodes compared with other high-performance electrodes at different temperatures. (c) DRT analyses for symmetrical cells featuring PBCR0.1C air electrodes at 650 °C under various partial pressures of oxygen (pO2). (d) pO2 dependence of Rp of the PBCR0.1C air electrode at LF, IF, and HF regions. (e) DRT profiles for symmetrical cells featuring PBCR0.1C air electrodes tested at 650 °C for EIS at different pH2O. (f) pH2O dependence of Rp of the PBCR0.1C air electrode at different frequency ranges. (g) Rp stability of PBCR0.1C and PBCC air electrode in humid air (3 vol% H2O) at 650 °C under OCV conditions; insets correspond to EIS of PBCR0.1C and PBCC. (h) DRT of the EIS of PBCR0.1C air electrode at different testing times during stability test.

Fig. 3. Electrical conductivity and surface properties of the PBCR0.1C. (a) The electrical conductivity of dense PBCR0.1C and PBCC bars in dry air. (b) The XPS profiles of Co 2p3/2 and Ba 3d5/2 for PBCR0.1C. (c) The XPS profile of O 1s for the PBCR0.1C sample. (d) FTIR spectra of PBCR0.1C powders that have been steam-treated.

Fig. 4. Electrochemical performance and Microstructure evaluation of single cells. (a) I-V-P curves of PBCR0.1C single cell (FC mode). (b) The EIS curves of the PBCR0.1C single cell under OCV conditions. (c) I-V curves of PBCR0.1C single cell (EL mode). (d) Comparison of PPD with other high-performance electrodes. (e) Comparison of the current density with various electrode materials in EL mode (1.3 V). (f) A cross-sectional scanning electron micrograph of a PBCR0.1C single cell.

Fig. 5. Durability test and Faradaic efficiency of single cells. (a) Durability test of the PBCR0.1C single cells in FC/EL mode at 650 °C. (b) Cycling durability test of R-PCEC equipped PBCR0.1C air electrode at 650 °C. FE (c) and corresponding H2 generation rates (d) at different steam concentrations (10 and 30 vol% H2O) and 600 °C with various current densities (-0.5, -0.75, and -1 A cm?2). FE (e) and corresponding H2 generation rates (f) at different steam concentrations (10 and 30 vol% H2O) at 650 °C with various current densities (-0.5, -0.75, and -1 A cm?2).

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