Rational Design of Ruddlesden-Popper Perovskite Ferrites as Air Electrode for Highly Active and Durable Reversible Protonic Ceramic Cells

doi:10.1007/s40820-024-01397-2

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Abstract

Reversible protonic ceramic cells (RePCCs) hold promise for efficient energy storage, but their practicality is hindered by a lack of high-performance air electrode materials. Ruddlesden-Popper perovskite Sr₃Fe₂O_7−δ (SF) exhibits superior proton uptake and rapid ionic conduction, boosting activity. However, excessive proton uptake during RePCC operation degrades SF’s crystal structure, impacting durability. This study introduces a novel A/B-sites co-substitution strategy for modifying air electrodes, incorporating Sr-deficiency and Nb-substitution to create Sr_2.8Fe_1.8Nb_0.2O_7−δ (D-SFN). Nb stabilizes SF's crystal, curbing excessive phase formation, and Sr-deficiency boosts oxygen vacancy concentration, optimizing oxygen transport. The D-SFN electrode demonstrates outstanding activity and durability, achieving a peak power density of 596 mW cm⁻² in fuel cell mode and a current density of − 1.19 A cm⁻² in electrolysis mode at 1.3 V, 650 °C, with excellent cycling durability. This approach holds the potential for advancing robust and efficient air electrodes in RePCCs for renewable energy storage.

Key words： Reversible protonic ceramic cells Air electrode Ruddlesden-Popper perovskite Hydration Oxygen reduction reaction

Received: 27 December 2023 Published: 22 April 2024

Corresponding Authors: Yufei Song, Meng Ni

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	Na Yu
	Idris Temitope Bello
	Xi Chen
	Tong Liu
	Zheng Li
	Yufei Song
	Meng Ni

Cite this article:

Na Yu,Idris Temitope Bello,Xi Chen, et al. Rational Design of Ruddlesden-Popper Perovskite Ferrites as Air Electrode for Highly Active and Durable Reversible Protonic Ceramic Cells[J]. Nano-Micro Letters, 2024, 16(1): 177-.

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https://www.qk.sjtu.edu.cn/nml/EN/10.1007/s40820-024-01397-2 OR https://www.qk.sjtu.edu.cn/nml/EN/Y2024/V16/I1/177

Fig. 1 Working principle of RePCC combined with renewable energy

Fig. 2 Structural characterization of S3−yFNx compositions. a XRD patterns indexed to standard RP structure. b EDX confirming elemental composition. c STEM showing nanoparticle morphology. d, e HR-TEM verifying crystallinity and d-spacings. f EDX mapping demonstrating uniform Nb incorporation

Fig. 3 Impact of Nb doping and Sr deficiency on S3−yFNx properties. a Electrical conductivity showing the semiconducting-metallic transition. b XPS valence state quantification of Fe 2p. c Oxygen non-stoichiometry (δ) determination via TGA and iodometric test. d Oxygen surface exchange coefficient (kchem) and oxygen bulk diffusion coefficient (Dchem) from ECR. e Schematic diagram of the dual modification strategy

Fig. 4 Electrochemical performance and reaction kinetics of the S3−yFNx electrodes. a Schematic diagram of the ORR process in the humid air. b Arrhenius plots of D-SFN electrode under different pH2O. c Impact of pH2O on EIS of D-SFN electrode. d DRT revealing rate-determining steps. e Arrhenius plots quantifying ASR analyzed by S3−yFNx|BZCYYb|S3−yFNx symmetrical cells. f Performance comparison of D-SFN electrode with the reported electrodes in the humid air. g DRT curves in the humid air. h Free energies of the ORR reaction on the surface of S3−yFNx

Fig. 5 Stability assessments of S3−yFNx electrodes. a Perovskite formation energy (Eform) of S3−yFNx. b ASR evolution during humid air symmetrical cell testing. c powder XRD processed in dry air. d powder XRD processed in the humid air. e TEM of D-SFN powders treated in the humid air for 150 h. f Fe 2p XPS spectra of D-SFN before and after hydration for 150 h. g EIS evolution of SF and D-SFN electrode. h DRT analysis of EIS curves in g

Fig. 6 Electrochemical performance of Ni-BZCYYb|BZCYYb|D-SFN single cell. a Fuel cell power density curves under H2/ humidified air. b Benchmarking peak power density against recently reported high-performance PCFCs. c Long-term stability under PCFC mode (at 0.8 V). d Polarization curves exhibiting high current density under H2/humidified air. e Benchmarking electrolysis performance against state-of-the-art PCECs at 1.3 V. f Durability under PCEC mode (at 1.3 V). g Outstanding cyclic stability over 160 h with 23 reversal cycles between fuel cell (0.8 V) and electrolysis (1.3 V) modes

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