Scandium and phosphorus co-doped perovskite oxides as high-performance electrocatalysts for the oxygen reduction reaction in an alkaline solution

doi:10.1016/j.jmst.2019.09.007

Abstract

Abstract:

The requirement for a sustainable and renewable energy has inspired substantial interests in designing and developing earth-abundant and high-effectiveness electrocatalysts/electrodes for fuel cells and metal-air batteries, in which oxygen reduction reaction (ORR) plays a crucial role. Perovskite oxides have acquired rapid attention as ORR electrocatalysts to replace noble-metal-based catalysts owing to their intrinsic electrocatalytic activity, compositional and structural flexibility. Herein, we report a new Sc and P co-doped perovskite oxide (La_0.8Sr_0.2Mn_0.95Sc_0.025P_0.025O_3-_δ, LSMSP) as an active and robust electrocatalyst for the ORR in an alkaline solution. LSMSP electrocatalyst shows superior ORR activity and stability than those of pristine La_0.8Sr_0.2MnO_3-_δ (LSM), Sc-doped LSM and P-doped LSM due to the optimized average valence of Mn ions, the large surface area, the smaller particle size and the synergetic effect introduced by the co-doping. Moreover, compared to the benchmark Pt/C electrocatalyst, LSMSP electrocatalyst displays comparable ORR activity and superior durability. These above results suggest that the co-doping strategy of Sc and P into perovskites is a useful method to design high-performance electrocatalysts for the ORR, which can be used in other electrocatalysis-based applications.

Key words: Oxygen reduction reaction, Perovskite oxide, Co-doping, Electrocatalyst, Synergetic effect

Meigui Xu, Hainan Sun, Wei Wang, Yujuan Shen, Wei Zhou, Jun Wang, Zhi-Gang Chen, Zongping Shao. Scandium and phosphorus co-doped perovskite oxides as high-performance electrocatalysts for the oxygen reduction reaction in an alkaline solution[J]. J. Mater. Sci. Technol., 2020, 39: 22-27.

Figures/Tables 6

Fig. 1. (a) XRD patterns and (b) magnified region at 2θ = 31°?34° of La0.8Sr0.2MnO3-δ, La0.8Sr0.2Mn0.95P0.05O3-δ, La0.8Sr0.2Mn0.95Sc0.05O3-δ and La0.8Sr0.2Mn0.95Sc0.025P0.025O3-δ samples.

Fig. 2. SEM images of (a) La0.8Sr0.2MnO3-δ, (b) La0.8Sr0.2Mn0.95P0.05O3-δ, (c) La0.8Sr0.2Mn0.95Sc0.05O3-δ, and (d) La0.8Sr0.2Mn0.95Sc0.025P0.025O3-δ samples.

Fig. 3. EDX profiles of (a) La0.8Sr0.2Mn0.95Sc0.05O3-δ, (b) La0.8Sr0.2Mn0.95P0.05O3-δ, and (c) La0.8Sr0.2Mn0.95Sc0.025P0.025O3-δ samples.

Fig. 4. (a) Linear sweep voltammetry curves of La0.8Sr0.2MnO3-δ, La0.8Sr0.2Mn0.95P0.05O3-δ, La0.8Sr0.2Mn0.95Sc0.05O3-δ, La0.8Sr0.2Mn0.95Sc0.025P0.025O3-δ and Pt/C at 1600 rpm in O2-saturated 0.1 M KOH, (b) EIS spectra of perovskite samples obtained at a frequency range of 100 kHz to 0.1 Hz at 0.27 V vs. RHE under a 10 mV AC potential bias in O2-saturated 0.1 M KOH, (c) The n values of various perovskite electrocatalysts based on the K-L equation at 0.35 V vs. RHE.

Fig. 5. (a) Mn 2p and (b) O 1s XPS spectra of La0.8Sr0.2MnO3-δ, La0.8Sr0.2Mn0.95P0.05O3-δ, La0.8Sr0.2Mn0.95Sc0.05O3-δ and La0.8Sr0.2Mn0.95Sc0.025P0.025O3-δ samples.

Fig. 6. Linear sweep voltammetry curves of (a) La0.8Sr0.2MnO3-δ, (b) La0.8Sr0.2Mn0.95P0.05O3-δ, (c) La0.8Sr0.2Mn0.95Sc0.05O3-δ, (d) La0.8Sr0.2Mn0.95Sc0.025P0.025O3-δ and (e) Pt/C obtained before and after 500 potential cycles, (f) I?t curves of various electrocatalysts in O2-saturated 0.1 M KOH.

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